Oscillatory reaction as a system detector for doped and undoped phosphate tungsten bronzes

Abstract

Phosphate tungsten bronzes, obtained by thermal treatment, are insufficiently investigated bronzes and there is scarce literature data on their chemical behavior and structure. Due to high-sensitivity of the Briggs-Rauscher (BR) reaction to addition of different analytes, this oscillatory reaction presents a potentially important chemical system for investigation and characterization of phosphate-tungsten bronzes, doped and undoped. The reaction mixture for the oscillatory BR reaction typically consists of H2O2, HClO4, KIO3, Mn(II) (catalyst), and CH2(COOH)2 (malonic acid, as an organic substrate). This paper deals with phosphate tungsten bronzes (PWB) and lithium doped phosphate tungsten bronzes (LiPWB) and their effects on the Briggs-Rauscher reaction dynamics. It is shown that the addition of phosphate tungsten bronzes decreases the oscillatory period length in this reaction. Furthermore, the obtained results show that PWB has a stronger influence on the BR reaction dynamics then LiPWB. In both cases, the oscillatory period is a linear function of the added bronze mass. The obtained linear functions can be successfully used for determination of the unknown bronze mass. Furthermore, due to different slopes of these functions, the Briggs-Rauscher reaction can be used as a system-detector for lithium doped and undoped phosphate tungsten bronzes. In order to elucidate the mechanism of bronze action, the inductively coupled plasma optical emission spectrometry (ICP-OES) was used to measure the total contents of K, Mn, W, Li. The aliquots of the above solution (i.e. CH2(COOH)2, MnSO4, HClO4, KIO3 but without H2O2) with the identical masses of PWB and LiPWB were examined. For the sake of comparison, contents of the metals in the solution without the bronze addition were measured, as well. Results obtained by the ICP-OES analysis show that the bronze structure is disturbed in the strong oxidizing environment (iodate in acidic solution) so that both, tungsten and lithium, leach into the BR solution. Accordingly, the proposed mechanism of the bronze action is probably by the reaction of tungsten ion with hydrogen-peroxide resulting in formation of a tungsten-peroxo complex. This complex is a stronger oxidizing agent then hydrogen peroxide itself. Thus, formation of the tungsten-peroxo complex potentially affects the kinetics of the Briggs-Rauscher reaction. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. 172015, Grant no. III45001 and Grant no. III45014]

Keywords

• bronzes
• phosphate tungsten bronzes
• oscillatory reaction
• Briggs-Rauscher reaction
• nonlinear phenomena