This paper reports dynamical behaviour of the palladium catalysed oxidative carbonylation reaction of phenylacetylene in a homogeneous catalytic system (PdI₂–KI–O₂–NaOAc in methanol). The dynamics of this system is studied through the simultaneous oscillations in pH and reaction exotherm (Q_r) in a calorimeter. The objective of the study is to contribute towards understanding the reaction kinetics underlying the oscillation generation. To achieve this goal, the reaction is perturbed by methanol and phenylacetylene at different phases and the dynamics is characterised according to the phases of the pH oscillations. In addition, concentration profiles of reactants and products in a larger period pH oscillation at lower reactor temperature are reported. Other observations, such as quasiperiodic pH oscillations in response to changes in air-flow rate and pH oscillations after the incidence of white light are presented.

The dynamical behaviour of the reaction system is analysed by nonlinear dynamical tools. The pH oscillations in response to single pulse perturbations by methanol and phenylacetylene are represented by phase transition curves (PTC's). The dynamical characteristics of the system under periodic perturbations are simulated from iterations of the PTC's for a range of forcing time intervals. Resonance regions are identified for specific forcing periods and are illustrated by respective firing number plots. The firing number sequences denote devil's staircase like dependence on the perturbation time intervals.