Kinetics of peracetic acid decomposition: Part I: Spontaneous decomposition at typical pulp bleaching conditions

Abstract

Peracetic acid may become one of alternative non-chlorine bleaching chemicals in the production of fully bleached chemical pulps. In this paper, the stability of peracetic acid was studied in an aqueous solution under conditions most likely encountered in the industrial processes. It was found that three potential reactions, namely i) the spontaneous decomposition, ii) the hydrolysis and iii) the transition metal catalyzed decomposition, are responsible for the consumption of peracetic acid. Furthermore, the kinetics of the spontaneous decomposition was developed. It was found that the reaction follows a second-order kinetics with the maximum rate at pH 8.2, which is the pK, of peracetic acid. Finally, the developed kinetic equation can describe very well the experimental results obtained in this study as well as the earlier data from Koubek (1964).L'acide peracetique pourrait Ctre une des substances de blanchiment sans chlore possible pour produire des pites chimiques completement blanchies. Dans cet article, on a etudie la stabilite de I'acide peracetique dans une solution aqueuse, dans les conditions les plus souvent rencontrees dans les procedes industriels. On a trouve que les trois reactions potentielles, soient la decomposition spontanee, I'hydrolyse et la decomposition catalysee des metaux de transition, etaient responsables de la consommation de l'acide peracetique. En outre, on a etabli la cinidique de la decomposition spontanee. On a trouve que la reaction suivait une cinetique du second ordre avec une vitesse maximale a un pH de 8,2, qui est le pK de I'acide peracetique. Enfin, I'equation cinetique etablie peut decrire parfaitement les resultats experimentaux obtenus dans cette etude ainsi que les anciennes donnees de Koubek (1964).Keywords: kinetics, peracetic acid, spontaneous decomposition, hydrolysis, pulp bleaching.Environmental concerns and market pressure are forcing the pulp and paper industry to explore alternatives to conventional chlorine containing bleaching chemicals. Recent results have shown that peracetic acid is a less capital intensive, easily retrofit and highly selective TCF bleaching agent when it is being used under the optimum conditions (Troughton et al., 1994).Peracetic acid is the mono-acetyl derivative of hydrogen peroxide and has a single acidic proton with a pK, of 8.2 at 25OC (Koubek et al., 1963). It is usually prepared by mixing acetic acid and hydrogen peroxide with sulfuric acid as a catalyst (Swern, 1970). This manufacturing process is reversible and thus an equilibrium mixture of reactants and products is normally obtained. The high purity peracetic acid can be obtained by distillation.Peracetic acid decomposes spontaneously in aqueous solution to give acetic acid and oxygen (Swern, 1970). Transitional metal ions such as cobalt and manganese ions catalyze the peracetic acid decomposition; however, the catalytic effect could be virtually eliminated by the addition of a suitable chelating agent (Koubek et al., 1963). In addition, peracetic acid can be hydrolyzed to fo...

Anin vitroandin vivoevaluation of peroxyacetic acid as an alternative sanitizer for wine barrels

“…Baldry (1983) exposed S. cerevisiae to different concentrations of PAA, however different temperatures and pH were used (5.0, 6.5 and 8.0), versus our experiment, where pH was not a factor to control since only deionized water was used to prepare the PAA solutions that were added to the flasks (in vitro experiments) and where temperature was stable during the whole time of our experiment. Baldry (1983) found that the efficacy of PAA against two strains of S. cerevisiae decreases with increasing pH, since when alkalinity of the solution increases, peracetic acid is hydrolyzed to form acetic acid and hydrogen peroxide (Yuan et al, 1997). Accordingly, Baldry (1983) found that resistance among genera (particularly between Z. bailii and S. cerevisiae) is variable, this latter aspect also found in our experiments.…”

“…PAA solutions are produced from the reaction of acetic acid or acetic anhydride with hydrogen peroxide in the presence of sulfuric acid, which functions as a catalyzing agent (Vandekinderen et al, 2009). In spontaneous decomposition, peracetic acid is decomposed to form acetic acid and oxygen, thus representing a loss of oxidation power (Yuan et al 1997). It acts primarily on lipoproteins in the cell membrane, and it may be equally effective against outer membrane lipoproteins (Silveira et al, 2008).…”

Peracids in water treatment: A critical review

“…Furthermore, the peracid formulation, namely the peracid/H 2 O 2 ratio and possible stabilizers have an effect on the decomposition rate [104]. In a concentrated solution, the decomposition of peracid occurs by three mechanisms: hydrolysis, spontaneous decomposition, and transition-metal catalyzed decomposition (Reactions 9, 10, and 11, respectively) [106][107][108]. The kinetics and exact reaction mechanisms of the spontaneous decomposition and hydrolysis were presented by Zhao et al [36,109].…”

Fractional determination of peracetic acid and hydrogen peroxide at deposited gold enriched in the Au(1 1 1) domain

“…This finding could be explained as follows; crystallographic orientation is well known to significantly affect the electrocatalytic properties of electrodes toward several electrochemical reactions [26][27][28][29]. For instance, the oxygen reduction reaction (ORR), and consequently H 2 O 2 reduction, is inherently dependent on the crystallographic orientation of the Au electrode [30]. The present study is the first report regarding the dependence of PAA reduction on the crystallographic orientation of gold electrode.…”