Kinetics and mechanisms of chlorine transfer from chloramine to amines in aqueous medium

The kinetics and the equilibrium constant of the chlorine transfer reaction between monochloramine NH₂Cl and the amines: C₂H₅NH₂, (CH₃)₂CHNH₂, (CH₃)₂NH, and (C₂H₅)₂NH are investigated by spectrophotometry in aqueous medium at 25°C, in the pH range from 8 to 13 and for an ionic strength equal to 1.03 ± 0.05M. For a concentration of total ammonia equal to 1M, the observed rate constant is pH independent below 8 and above 12.8 and reaches a maximum located between the pK_as of NH₄⁺ and RR'NH₂⁺. From these results and those obtained earlier for NH₂Cl and CH₃NH₂, the reaction is shown to involve an interaction between neutral molecules NH₂Cl and RR'NH, subject to general acid catalysis. The ability of an interaction corresponding to a specific catalysis and involving NH₃Cl⁺ and RR'NH rather than NH₂Cl and RR'NH₂⁺ is also discussed. The activation parameters are given for each reaction.