Chain carrier

In step (1) and step (2) there is an increase from one to two chain carriers . (For brevity, step (x) is used to refer to equation (A3.14.V) tliroughout.) Under typical experimental conditions close to the first and second explosion limits (see section A3.14.2.3). step (2) and step (3) are fast relative to the rate detemiining step (1). 

Styrene—butadiene block copolymers are made with anionic chain carriers, and low molecular weight PS is made by a cationic mechanism (110). Analytical standards are available for PS prepared by all four mechanisms (see Initiators). 

Hydrogen haHde addition to vinyl chloride in general yields the 1,1-adduct (50—52). The reactions of HCl and hydrogen iodide [10034-85-2], HI, with vinyl chloride proceed by an ionic mechanism, while the addition of hydrogen bromide [10035-10-6], HBr, involves a chain reaction in which a bromine atom [10097-32-2] is the chain carrier (52). In the absence of a transition-metal catalyst or antioxidants, HBr forms the 1,2-adduct with vinyl chloride (52). HF reacts with vinyl chloride in the presence of stannic chloride [7646-78-8], SnCl, to form 1,1-difluoroethane [75-37-6] (53). 

The second step is a -scission, the breaking of a carbon—carbon bond P to the charged carbon. The sum of the two reactions is the stoichiometry of the overall cracking reaction R H — RH + olefin. R+, a relatively stable carbenium ion such as the /-butyl cation, is a chain carrier. The role of the catalyst is to donate the proton to start the chain. This is a greatiy simplified representation. 

The chain carriers CIO9 and CIO3 are assumed to attain steady state. Then,... 

MILLER - SNYDER Aiyl Cyanide Synthesis Synthesis of benzonitnies from aldehydes via oxime ethers Formation of p-cyanophenol from p nrtrobenzaldoxime and p-nitiobenzonitnle (used as a sometimes recyclable chain carrier)... 

The reaction between hydrogen and bromine is the first step in the initiation reaction in which the chain carriers are formed. The thermal hydrogen bromine reaction begins with the initiation reaction ... 

An example of cleavage ol the sulfur-oxygen bond in trifluoromethane-sulfonic ester has been reported Tnfluororaethyl triflate reacts with neutral or anionic nucleophiles with elimination of carbonyl difluoride and formation of trifluoromethanesulfonyl fluoride [57] (equation 32) The mechanism of this reaction involves elimination of fluoride ion, which is a chain carrier in the substitution of fluorine for the trifluoromethoxy group... 

These polymers could not be crystallized, despite their apparent stereoregularity, probably because of the sterically-hindered character of the chains. It was proposed by Farina and Bressan62 that the chain growth was stereoregulated by the optically active anion of the ion-paired chain carrier. Further studies63 showed that the first portion of the polymer produced in a given reaction always possessed a less regular structure than later portions, unless the reaction was started in the presence of previously prepared polymer. This observation was interpreted as evidence for the pre-... 

The effect of common-anion salts and of added water showed, however, that ionic chain carriers must also be present in these systems. These observations, coupled with experiments where dilute solutions of the monomers were treated with excess of acid and the reactions followed by ultraviolet spectroscopy, produced sufficient information about the initiation reaction pattern and thus completed the overall kinetic and mechanistic approach. 

Another chain mechanism also needs to be considered. The initiation step is the same, but now the chain carriers are M and MOO. ... 

Although the first reaction is of an ordinary sort, the next two are unusual in that one propagating intermediate is converted into two. These are branching reactions. As each occurs, the total rate speeds up. When that happens, even more branching occurs, and so on. If unchecked, the exponential growth of chain carriers leads to explosion, just as in nuclear chain reactions. 

The chlorine atoms generated in this first step are quite reactive in the presence of oxalic acid they can act as chain carriers for reaction (1). The experiment was performed by adding to a solution of CP and H2C204 a very low concentration of Fe2i at a constant rate R. Since reaction (3) is very fast, the rate of generation of Cl is equal to R. The chain-carrying steps are presumed to be... 

The free radical additions of sulfonyl halides to alkenes, catalyzed by light or typical chemical radical initiators (In), were first investigated in the 1950s69. The products which are / -halo sulfones (22) were obtained via a chain reaction in which RSO j acts as the chain carrier, namely61-62,70,71... 

In the mechanisms considered so far, there have only been one or two intermediates. In a chain reaction, a highly reactive intermediate reacts to produce another highly reactive intermediate, which reacts to produce another, and so on (Fig. 13.19). In many cases, the reaction intermediate—which in this context is called a chain carrier—is a radical, and the reaction is called a radical chain reaction. In a radical chain reaction, one radical reacts with a molecule to produce another radical, that radical goes on to attack another molecule to produce yet another radical, and so on. The ideas presented in the preceding sections apply to chain reactions, too, but they often result in very complex rate laws, which we will not derive. 

Once chain carriers have been formed, the chain can propagate in a reaction in which one carrier reacts with a reactant molecule to produce another carrier. The elementary reactions for the propagation of the chain are... 

The chain carriers—radicals here—produced in these reactions can go on to attack other reactant molecules (H2 and Br2), thereby allowing the chain to continue. The elementary reaction that ends the chain, a process called termination, takes place when chain carriers combine to form products. Two examples of termination reactions are ... 

FIGURE 17.24 A self-sustaining chain reaction, in which neutrons are the chain carriers, takes place when induced fission produces more than one neutron per fission event. These newly produced neutrons can stimulate fission in increasingly greater numbers of other nuclei. 

Nuclear energy can be extracted by arranging for a nuclear chain reaction to take place in a critical mass of fissionable material. with neutrons as the chain carriers. A moderator is used to reduce the speeds of the neutrons in a reactor that uses fissile material. 

Due to their weak P-H bonds (-370 kj mol"0 [2] and the high rate constants for the transfer of the P-H hydrogen [3] (/c=1.5 10 L rnoL s" for Ph2PH and k=5,0 10 L mol s for (c-hexyl)2PH), diaryl and dialkyl phosphines present a high interest as H-donors. Since the corresponding phosphinyl radicals are good chain carriers [4,5], diaryl and dialkyl phosphines can be added to olefinic or acetylenic compounds through radical chain reactions. Simpkins et al. [6] used... 

R2P(0)H) and phosphonates (R02P(0)H) as hydrogen atom donors and the corresponding phosphonyl radicals as chain carriers (Scheme 3). 

Fluorinated phosphonates exhibit interesting properties as enzyme inhibitors, chelating agents or as fuel cell electrolytes [29] however, only few methods of preparation for these compounds are available. Burton et al. [30] developed several methods to prepare fluorinated phosphates which involve phosphonyl, and likely phosphoranyl radicals as chain carriers (Scheme 11). 

Scheme 11 Preparation of fluorinated phosphonates involving phosphonyl and phospho-ranyl radicals as chain carriers...

Scheme 37 Radical chain desulfurization involving phosphoranyl radicals as chain carriers. Reprinted with permission from [74]. Copyright 1998 Pergamon Press...

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