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The Role of Interfacial Reactions in Determining Plasma–Liquid Chemistry

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Abstract

In this work, we investigate the production of highly oxidative species in solutions exposed to a self-pulsed corona discharge in air. We examine how the properties of the target solution (pH, conductivity) and the discharge power affect the discharge stability and the production of H2O2. Indigo carmine, a common organic dye, is used as an indicator of oxidative strength and in particular, hydroxyl radical (OH·) production. The observed rate of indigo oxidation in contact with the discharge far exceeds that predicted from reactions based on concentrations of species measured in the bulk solution. The generation of H2O2 and the oxidation of indigo carmine indicate a high concentration of highly oxidizing species such as OH· at the plasma–liquid interface. These results indicate that reactions at the air plasma–liquid interface play a dominant role in species oxidation during direct non-equilibrium atmospheric pressure plasma treatment.

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Notes

  1. In simple experiments in which methyl red solutions (buffered to pH 7.4) were treated with NEAPP, no color change (indicating a gradient in pH) was observed near the surface or anywhere in solution. Solutions were treated with NEAPP until the buffer was overcome, at which point the color uniformly changed from yellow to red. This is in contrast to experiments performed by Witzke et al. [79] (in the absence of convection), in which spatial gradients in pH were observed at the plasma-liquid interface. This suggests that any gradients in pH that exist are restricted to very near the surface.

  2. The rate at which 1O2 is quenched (reduced to the triplet state) by indigo carmine is 3.2 × 108 M−1 s−1 per the results of Gandra et al. [76]. Moreover, the quenching of 1O2 observed in these experiments was stated to occur through “physical quenching”, or processes that convert 1O2 to 3O2 by reducing the energy state of indigo carmine rather than changing its structure (“chemical quenching”). Oxidation products of indigo carmine were only observed after extended irradiation periods (several hours of 1O2 production).

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  1. Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA, USA

    Carly E. Anderson, Nico R. Cha, Douglas S. Clark & David B. Graves

  2. Department of Nuclear Engineering, North Carolina State University, Raleigh, NC, USA

    Alexander D. Lindsay

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Anderson, C.E., Cha, N.R., Lindsay, A.D. et al. The Role of Interfacial Reactions in Determining Plasma–Liquid Chemistry. Plasma Chem Plasma Process 36, 1393–1415 (2016). https://doi.org/10.1007/s11090-016-9742-1

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