Effects of Micellar Aggregates on the Kinetics and Mechanism of the Reaction between 4‐Nitrobenzenediazonium Ions and Some Amino Acids

Abstract

AbstractWe have explored the kinetics and mechanism of the reaction between 4‐nitrobenzenediazonium ions (4NBD), and the hydrophilic amino acids (AA) glycine and serine in the presence and absence of sodium dodecyl sulfate (SDS) micellar aggregates by means of UV/VIS spectroscopy. The observed rate constants kobs were obtained by monitoring the disappearance of 4NBD with time at a suitable wavelength under pseudo‐first‐order conditions. In aqueous acid (buffer‐controlled) solution, in the absence of SDS, the dependence of kobs on [AA] was obtained from the linear relationship found between the experimental rate constant and [AA]. At a fixed amino acid concentration, kobs values show an inverse dependence on acidity in the range of pH 5–6, suggesting that the reaction takes place through the nonprotonated amino group of the amino acid. All kinetic evidence is consistent with an irreversible bimolecular reaction with k=2390±16 and 376±7 M−1 s−1 for glycine and serine, respectively. Addition of SDS inhibits the reaction because of the micellar‐induced separation of reactants originated by the electrical barrier imposed by the SDS micelles; kobs values are depressed by factors of 10 (glycine) and 6 (serine) on going from [SDS]=0 up to [SDS]=0.05M. The hypothesis of a micellar‐induced separation of the reactants was confirmed by 1H‐NMR spectroscopy, which was employed to investigate the location of 4NBD in the micellar aggregate: the results showed that the aromatic ring of the arenediazonium ion is predominantly located in the vicinity of the C(β) atom of the surfactant chain, and hence the reactive N$\rm{ _2^ + }$ group is located in the Stern layer of the micellar aggregate. The kinetic results can be quantitatively interpreted in terms of the pseudophase kinetic model, allowing estimations of the association constant of 4NBD to the SDS micelles.