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Mechanistic Notation and Rate Expressions

The generic mechanism above is denoted in electrochemical terminology as an E(C )J mechanism, that is, an initial electrochemical step (the radical cation generation), followed by polymer propagation via successive chemical (combination with monomer radical cation, proton loss) and electrochemical (oxidation to generate oligomeric radical cations) steps, and likely termination via a chemical step. The [Pg.107]

Representative electropolymerization chronoampero-grams and chronocoulograms. 5 2 After Reference [73], reproduced with permission. 5-3. 5-4 Courtesy of Ashwin -Ushas Corp., Inc. [Pg.109]

5-5 Electropolymerization CV for thiophene in acetonitrile, showing crossover (see text). After Reference [76], reproduced with permission. [Pg.110]

Solvent retention within the polymer matrix, as discussed in Chapter 3 for P(ANi), or alternatively, retention of solvent affinity sites , are important factors sometimes ignored by many workers. Thus, for instance, several poly (diphenyl amine) derivatives, when electropolymerized in acetonitrile or PC, will electrochemically cycle well only in the solvent of electropolymerization [36, 74, 67, 75]. Solvents may also be too nucleophilic besides its high solvation capability for even doped CPs, dimethyl formamide (DMF) is also a poor electropolymerization solvent due to high nucleophilicity if this is reduced with addition of protic solvents, electropolymerizations are observed [43]. Table 5-2 cited above has [43] summarized electropolymerization data for P(Py) in various solvents. [Pg.110]

In cases where the monomer has poor solubility in an otherwise ideal polymerization solvent such as acetonitrile, mixed solvents are used primarily to facilitate solubility. [Pg.110]


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