Reactions chain reaction steps

In any controlled chain reaction steps (a) to (c) are essentially present. However, in some chain reactions, a step, which may inhibit the process, may also be involved. This step is called inhibition step. For example, in Br2... 

This is an extremely important reaction to which we wiU refer throughout this book. It is responsible for all NO, formation in the atmosphere (the brown color of the air over large cities) as well as nitric acid and acid rain. This reaction only occurs in high-temperature combustion processes and in lightning bolts, and it occurs in automobile engines by free-radical chain reaction steps, which will be the subject of Chapter 10. It is removed from the automobile exhaust in the automotive catalytic converter, which wiU be considered in Chapter 7. 

Although CH2COCH3 is formed from CH and CH3COCH3, there is no subsequent major reaction of CH2COCH3 to regenerate CH, and so the mechanism proposed is not a chain reaction. Step 7 does regenerate CH, but it is not a major step in this photochemical reaction. 

Figure 15.5 Polymerase chain reaction step 1, separation of strands by heating (98°C) step 2, anneal primers (60°C) step 3, primer extension by polymerase.

The best known reaction implying anions and photoinduced electron transfer is the S l reaction. In this synthetically useful process a radical chain reaction (steps (9) to (11)) is running ArX is an electron accepting substrate, Nu is the nucleophile and ArNu is the substituted product ... 

The polymerization runs through the chain-reaction steps, that is, initiation, propagation and termination. After completion of the polymerization, the template is removed from the polymer by extraction (step 3). The resulting polymer is then able to selectively rebind the template molecule (step 4). 

The main difference between the kinetics in this regime and in the one considered above is the noticeable competition between reactions (a) and (J), as was illustrated in the case of the t] = 0-33 exponential growth data in Fig. 2.8. By equations (2.11) and (2.12), this results in being keenly dependent upon the product of [O2] and the difference Ika — A /[M]). As a function of gas pressure at a given temperature, t( departs radically from inverse proportionality to density and in fact exhibits a minimmn, approximately at k/[M] = ka- Correspondingly the temperature dependence of is different for each density of reactants and diluents, and its correspondence with equation (2.15) and the activation energies of elementary chain reaction steps vanishes. Data demonstrating this behaviour are exhibited in Fig. 2.10, as individual curves of log t vs 1 jT for each postshock pressure. 

Free radical polymerization can be conveniently codified according to the classical chain reaction steps of initiation, propagation, transfer and termination. In cases where a significant solvent effect is operative then the effect is normally exerted in all of these steps. However, for the purpose of facilitating discussion this chapter is broken down into these specific reaction steps. 

The photoinduced photochemical substitution reactions of pentafluoronitrobenzene with several nucleophiles in aqueous media and the electrochemical detection of aromatic radical anions are taken as evidence for the presence of radical anion intermediates within the radical chain reaction steps. - ... 

The first stage, chain initiation, is the dissociation of chlorine molecules into atoms this is followed by two chain propagation reactions. Two molecules of hydrogen chloride are produced and the ejected chlorine atom is ready to react with more hydrogen. The final steps, chain termination, stop the reaction. Chain reactions are important in certain types of free-radical POLYMERIZATION reactions. 

After the primary step in a photochemical reaction, the secondary processes may be quite complicated, e.g. when atoms and free radicals are fcrnied. Consequently the quantum yield, i.e. the number of molecules which are caused to react for a single quantum of light absorbed, is only exceptionally equal to exactly unity. E.g. the quantum yield of the decomposition of methyl iodide by u.v. light is only about 10" because some of the free radicals formed re-combine. The quantum yield of the reaction of H2 -f- CI2 is 10 to 10 (and the mixture may explode) because this is a chain reaction. 

In practice side reactions intervene to reduce the efficiency of the propagation steps The chain sequence is interrupted whenever two odd electron species combine to give an even electron product Reactions of this type are called chain terminating steps Some commonly observed chain terminating steps m the chlorination of methane are shown m the following equations... 

Cation (Section 1 2) Positively charged ion Cellobiose (Section 25 14) A disacchande in which two glu cose units are joined by a 3(1 4) linkage Cellobiose is oh tamed by the hydrolysis of cellulose Cellulose (Section 25 15) A polysaccharide in which thou sands of glucose units are joined by 3(1 4) linkages Center of symmetry (Section 7 3) A point in the center of a structure located so that a line drawn from it to any element of the structure when extended an equal distance in the op posite direction encounters an identical element Benzene for example has a center of symmetry Cham reaction (Section 4 17) Reaction mechanism m which a sequence of individual steps repeats itself many times usu ally because a reactive intermediate consumed m one step is regenerated m a subsequent step The halogenation of alkanes is a chain reaction proceeding via free radical intermediates... 

Propagation steps (Section 4 17) Elementary steps that repeat over and over again in a chain reaction Almost all of the products in a chain reaction arise from the propagation steps... 

Termination steps (Section 4 17) Reactions that halt a chain reaction In a free radical chain reaction termination steps consume free radicals without generating new radicals to continue the chain... 

Step-growth polymerizations can be schematically represented by one of the individual reaction steps VA + B V —> Vab V with the realization that the species so connected can be any molecules containing A and B groups. Chain-growth polymerization, by contrast, requires at least three distinctly different kinds of reactions to describe the mechanism. These three types of reactions will be discussed in the following sections in considerable detail. For now our purpose is to introduce some vocabulary rather than develop any of these beyond mere definitions. The principal steps in the chain growth mechanism are the following ... 

High Peroxide Process. An alternative to maximizing selectivity to KA in the cyclohexane oxidation step is a process which seeks to maximize cyclohexyUiydroperoxide, also called P or CHHP. This peroxide is one of the first intermediates produced in the oxidation of cyclohexane. It is produced when a cyclohexyl radical reacts with an oxygen molecule (78) to form the cyclohexyUiydroperoxy radical. This radical can extract a hydrogen atom from a cyclohexane molecule, to produce CHHP and another cyclohexyl radical, which extends the free-radical reaction chain. 

An example of a commercial semibatch polymerization process is the early Union Carbide process for Dynel, one of the first flame-retardant modacryhc fibers (23,24). Dynel, a staple fiber that was wet spun from acetone, was introduced in 1951. The polymer is made up of 40% acrylonitrile and 60% vinyl chloride. The reactivity ratios for this monomer pair are 3.7 and 0.074 for acrylonitrile and vinyl chloride in solution at 60°C. Thus acrylonitrile is much more reactive than vinyl chloride in this copolymerization. In addition, vinyl chloride is a strong chain-transfer agent. To make the Dynel composition of 60% vinyl chloride, the monomer composition must be maintained at 82% vinyl chloride. Since acrylonitrile is consumed much more rapidly than vinyl chloride, if no control is exercised over the monomer composition, the acrylonitrile content of the monomer decreases to approximately 1% after only 25% conversion. The low acrylonitrile content of the monomer required for this process introduces yet another problem. That is, with an acrylonitrile weight fraction of only 0.18 in the unreacted monomer mixture, the low concentration of acrylonitrile becomes a rate-limiting reaction step. Therefore, the overall rate of chain growth is low and under normal conditions, with chain transfer and radical recombination, the molecular weight of the polymer is very low. 

One characteristic of chain reactions is that frequentiy some initiating process is required. In hydrocarbon oxidations radicals must be introduced and to be self-sustained, some source of radicals must be produced in a chain-branching step. Moreover, new radicals must be suppHed at a rate sufficient to replace those lost by chain termination. In hydrocarbon oxidation, this usually involves the hydroperoxide cycle (eqs. 1—5). 

Carbon-centered radicals generally react very rapidly with oxygen to generate peroxy radicals (eq. 2). The peroxy radicals can abstract hydrogen from a hydrocarbon molecule to yield a hydroperoxide and a new radical (eq. 3). This new radical can participate in reaction 2 and continue the chain. Reactions 2 and 3 are the propagation steps. Except under oxygen starved conditions, reaction 3 is rate limiting. 

An important descriptor of a chain reaction is the kinetic chain length, ie, the number of cycles of the propagation steps (eqs. 2 and 3) for each new radical introduced into the system. The chain length for a hydroperoxide reaction is given by equation (10) where HPE = efficiency to hydroperoxide, %, and 2/ = number of effective radicals generated per mol of hydroperoxide decomposed. For 100% radical generation efficiency, / = 1. For 90% efficiency to hydroperoxide, the minimum chain length (/ = 1) is 14. 

Autooxidation. Liquid-phase oxidation of hydrocarbons, alcohols, and aldehydes by oxygen produces chemiluminescence in quantum yields of 10 to 10 ° ein/mol (128—130). Although the efficiency is low, the chemiluminescent reaction is important because it provides an easy tool for study of the kinetics and properties of autooxidation reactions including industrially important processes (128,131). The light is derived from combination of peroxyl radicals (132), which are primarily responsible for the propagation and termination of the autooxidation chain reaction. The chemiluminescent termination step for secondary peroxy radicals is as follows ... 

Chemistry. Free-radical nitrations consist of rather compHcated nitration and oxidation reactions (31). When nitric acid is used in vapor-phase nitrations, the reaction of equation 5 is the main initiating step where NO2 is a free radical, either -N02 or -ON02. Temperatures of >ca 350° are required to obtain a significant amount of initiation, and equation 5 is the rate-controlling step for the overall reaction. Reactions 6 and 7 are chain-propagating steps. 

The degree of polymerization is controlled by the rate of addition of the initiator. Reaction in the presence of an initiator proceeds in two steps. First, the rate-determining decomposition of initiator to free radicals. Secondly, the addition of a monomer unit to form a chain radical, the propagation step (Fig. 2) (9). Such regeneration of the radical is characteristic of chain reactions. Some of the mote common initiators and their half-life values are Hsted in Table 3 (10). 

Although the alkylation of paraffins can be carried out thermally (3), catalytic alkylation is the basis of all processes in commercial use. Early studies of catalytic alkylation led to the formulation of a proposed mechanism based on a chain of ionic reactions (4—6). The reaction steps include the formation of a light tertiary cation, the addition of the cation to an olefin to form a heavier cation, and the production of a heavier paraffin (alkylate) by a hydride transfer from a light isoparaffin. This last step generates another light tertiary cation to continue the chain. 

Ethylene Dichloride Pyrolysis to Vinyl Chloride. Thermal pyrolysis or cracking of EDC to vinyl chloride and HCl occurs as a homogenous, first-order, free-radical chain reaction. The accepted general mechanism involves the four steps shown in equations 10—13 ... 

Autoca.ta.Iysis. The oxidation rate at the start of aging is usually low and increases with time. Radicals, produced by the homolytic decomposition of hydroperoxides and peroxides (eqs. 2—4) accumulated during the propagation and termination steps, initiate new oxidative chain reactions, thereby increasing the oxidation rate. 

In this reaction one ligand is inserted between the metal and another ligand, creating a site of coordinative unsaturation so that another reactant ligand can be associated with the metal. The insertion reaction accounts for the chain-growth steps of olefin polymeri2ation reactions. 

Chlorination of Methane. Methane can be chlorinated thermally, photochemicaHy, or catalyticaHy. Thermal chlorination, the most difficult method, may be carried out in the absence of light or catalysts. It is a free-radical chain reaction limited by the presence of oxygen and other free-radical inhibitors. The first step in the reaction is the thermal dissociation of the chlorine molecules for which the activation energy is about 84 kj/mol (20 kcal/mol), which is 33 kJ (8 kcal) higher than for catalytic chlorination. This dissociation occurs sufficiendy rapidly in the 400 to 500°C temperature range. The chlorine atoms react with methane to form hydrogen chloride and a methyl radical. The methyl radical in turn reacts with a chlorine molecule to form methyl chloride and another chlorine atom that can continue the reaction. The methane raw material may be natural gas, coke oven gas, or gas from petroleum refining. 

The individual steps in chain reactions involving radicals are characteristically of small activation energy, between about 10 and 50kJmol and so these reactions should occur at an immeasurably high rate at temperatures above 500 K (see Table 2.1), which is a low temperature for a useful combustion process. The overall rate of the process will tlrerefore depend mainly on the concentrations of tire radicals. 

These data suggest that both die chain reactions and die biinolecular reactions occur simultaneously in all systems but that the biinolecular reaction, which dominates the formation of HI, occurs only to a minor extent in the formation of HCl and HBr. To analyse the difference between these alternate mechanisms of hydrogen-halogen reactions, we should first consider die relative energies of each of the chain reaction steps for each system. The results for for... 

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