Journal of Physical Chemistry, Vol.100, No.22, 9389-9394, 1996
Photoresponse of the Ferrocyanide-Bromate-Sulfite Chemical Oscillator Under Flow Conditions
The photoresponse of the ferrocyanide-bromate-sulfite system, known as the pH oscillator, has been studied in the visible region. We have established a state diagram for this system spanned by the flow rate and irradiation light power in a continuous-flow stirred tank reactor. Photoinduced oscillations are observed for the system in the low-pH steady state in the dark, while the photoinhibition of oscillations are observed for the system oscillating in the dark. Batch experiments for its subsystems (the SO32--BrO3--H+, Fe(CN)(6)(4-)-BrO3--H+ and SO32--Fe(CN)(6)(3-)-H+ systems) have revealed that the positive feedback channels for H+ (the SO32--BrO3--H+ and SO32--Fe(CN)(6)(3-)-H+ reaction) are not sensitive at all to the visible light, while the negative feedback channel (the Fe(CN)(6)(4-)-BrO3--H+ reaction) is responsible for the observed photosensitivity of the whole system. We have confirmed that the enhanced formation of Fe(CN)(5)(H2O)(3-) from photoexcited HFe(CN)(6)(3-) is responsible for the photoacceleration of the negative feedback process.
Keywords:BELOUSOV-ZHABOTINSKII REACTION;BRIGGS-RAUSCHER REACTION;SYSTEMATIC DESIGN;AQUEOUS-SOLUTION;MECHANISM;HEXACYANOFERRATE(II);PHOTOINHIBITION;OXIDATION;KINETICS;ION