Peroxide mechanism graph

As a first example of the use of reaction mechanism graphs, consider the electrochemistry of molten carbonate fuel cell (MCFC) cathodes. These cathodes are typically nickel-oxide porous electrodes with pores partially filled with a molten carbonate electrolyte. Oxygen and carbon dioxide are fed into the cathode through the vacant portions of the pores. The overall cathodic reaction is 02 + 2C02 + 4e / 2C03=. This overall reaction can be achieved through a number of reaction mechanisms two such mechanisms are the peroxide mechanism and the superoxide-peroxide mechanism, and these are considered next. 

The relationship between the five peroxide mechanism reaction steps can be seen in the reaction mechanism graph in Figure 4. As defined above, each step occurs at one of the five nodes, and the directed edges give the forward direction for the mechanism. Current-carriers for the overall mechanism are in boxes, while carbonate ions that continue from one cycle to the next are circled. Dashed vertical lines represent interfaces between phases. Nodes on the gas-electrolyte interface represent reaction steps occurring at that interface nodes attached to the electrolyte-solid interface represent reaction steps occurring at sites on the surface of the solid phase. The location of each reaction on this reaction mechanism graph follows the description of the... 

Figure 4. Reaction mechanism graph for the peroxide mechanism reactions occur at dots, arrows show the forward direction for reactions, dashed lines separate phases, current-carriers are in boxes, and carbonate ions which continue from one cycle to the next are circled.

Figure 5. Superoxide-peroxide reaction mechanism graph notation and symbols as in Figure 4.

Figure 7. Reaction route graphs for the peroxide and superoxide-peroxide mechanisms reaction steps occur on directed edges nodes n, represent the component potentials, the difference between these potentials for adjacent nodes is the affinity of the associated reaction step and terminal nodes are open, intermediate nodes, closed.

Figure 8. Equivalent component-potential reaction route graph for the peroxide and superoxide-peroxide mechanisms.

The reaction route graphs, however, do have certain limitations. It is not in general possible, for example, to depict the physical location of the various reactions and species. It is not easy to distinguish on reaction route graphs that the peroxide ions, which must move across the electrolyte in the peroxide mechanism, exist only on the phase interfaces (gas-electrolyte and electrolyte-solid) in the superoxide-peroxide mechanism. This depiction is one of the strong points for reaction mechanism graphs. 

A kinetic study has been carried out in order to elucidate the mechanism by which the cr-complex becomes dehydrogenated to the alkyl heteroaromatic derivative for the alkylation of quinoline by decanoyl peroxide in acetic acid. The decomposition rates in the presence of increasing amounts of quinoline were determined. At low quinoline concentrations the kinetic course is shown in Fig. 1. The first-order rate constants were calculated from the initial slopes of the graphs and refer to reaction with a quinoline molecule still possessing free 2- and 4-positions. At high quinoline concentration a great increase of reaction rate occurs and both the kinetic course and the composition of the products are simplified. The decomposition rate is first order in peroxide and the nonyl radicals are almost completely trapped by quinoline. The proportion of the nonyl radicals which dimerize to octadecane falls rapidly with increase in quinoline concentration. The decomposition rate in nonprotonated quinoline is much lower than that observed in quinoline in acetic acid. 

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