Journal of Molecular Catalysis A: Chemical 271 (2007) 246252

Preparation of peracetic acid from hydrogen peroxide Part I: Kinetics for peracetic acid synthesis and hydrolysis
Xuebing Zhao a, , Ting Zhang a , Yujie Zhou b , Dehua Liu a,
a

Institute of Applied Chemistry, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China b Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China Received 28 August 2006; received in revised form 4 March 2007; accepted 5 March 2007 Available online 12 March 2007

Abstract A homogeneous kinetic model for preparation of peracetic acid (PAA) from acetic acid (AA) and hydrogen peroxide (HP) under the catalysis of sulfuric acid (SA) in the liquid phase was investigated. The kinetic equations of PAA synthesis and hydrolysis were given and the kinetic constants were estimated according to the experimental data by a simplex optimization method. It was found that the synthesis and hydrolysis of PAA were both rst-order reactions with respect to reactant concentrations and H+ concentration. Linear relationships were discovered between the observed rate constants and H+ concentrations at a certain temperature, with the slopes being corresponding intrinsic rate constants. The intrinsic activation energies of PAA synthesis and hydrolysis were 57.8 and 60.4 kJ mol1 , respectively. The mechanisms of PAA synthesis and hydrolysis were discussed. It has been proved that the rate-determining step in the synthesis of PAA is the reaction between H2 O2 with active carbonyl intermediary, and in the hydrolysis of PAA the reaction between water and corresponding active carbonyl intermediary. 2007 Elsevier B.V. All rights reserved.
Keywords: Peracetic acid; Hydrogen peroxide; Kinetics; Synthesis; Hydrolysis; Reaction mechanism

1. Introduction Peracetic acid (PAA) is a strong oxidant with reduction potential of 1.06 V, which is similar to that of traditional bleaching agent, chlorine dioxide [1]. It has been applied in disinfection [2,3], bleaching of textiles and pulps [47], epoxidation of olens [8,9], and so on. Recently, environmental concerns and market pressure are forcing the pulp and paper industry to explore alternatives to conventional chlorine containing chemicals. Some researches have shown that PAA is a less capital intensive, easily retrot and highly selective totally chlorine-free (TCF) bleaching agent when used under the optimum conditions [10]. Generally, PAA can be prepared in two ways, namely from hydrogen peroxide (HP) or by oxidation of acetaldehyde, and the latter can be operated in a liquid phase or vapour phase [11]. For many years the most commonly used method for preparing PAA has been the former way, either with acetic acid (AA)
Corresponding authors. Tel.: +86 10 62794742; fax: +86 10 62794742. E-mail addresses: [email protected] (X. Zhao), [email protected] (D. Liu). 1381-1169/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.molcata.2007.03.012

(see Eq. (1)) or with acetic anhydride (AAh) (see Eq. (2)). The AAhHP reaction is exothermic and difcult to control, and the possible formation of diacetyl peroxide leads to increased explosion hazards [11]. Therefore, the AAHP reaction is preferred in common preparation of PAA. This reaction is reversible and thus an equilibrium mixture of reactants and products is obtained. The rate at which equilibrium is achieved can be accelerated by adding a strong acid catalyst, usually sulfuric acid (SA):
2 4 CH3 COOH + H2 O2 CH3 COOOH + H2 O

H SO

(1) (2)

(CH3 CO)2 O + 2H2 O2 = 2CH3 COOOH + H2 O

Many studies have shown that the concentration of equilibrium PAA varied with the HP concentration and molar ratio of AA:HP. The charge of sulfuric acid used also differed from 0 to 9% [1113]. Some studies reported the decomposition or hydrolysis of peracetic acid in aqueous solutions [1417]. All of these researches have shown that the hydrolysis of PAA were rst-order with respect to PAA concentration. Only a few studies referred to the equilibrium kinetics of PAA preparation by the reaction of AA and HP [13,18]. However, in these researches no mathematical expressions for calculation of kinetic constants

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3. Results and discussion Nomenclature a A1 A2 bB CX CX0 Ea1 Ea2 I k1 k1obs k2 k2obs Ka,AcH KC,AcH T zB activity pre-exponential factor of peracetic acid synthesis (L mol2 h2 ) pre-exponential factor of peracetic acid hydrolysis (L mol2 h2 ) concentration of ion B (mol kg1 ) concentration of species X (mol L1 ) initial concentration of species X (mol L1 ) intrinsic activation energy of peracetic acid synthesis (kJ mol1 ) intrinsic activation energy of peracetic acid hydrolysis (kJ mol1 ) ionic strength intrinsic rate constant of peracetic acid synthesis (L mol2 h2 ) observed rate constant of peracetic acid synthesis (L mol1 h1 ) intrinsic rate constant of peracetic acid hydrolysis (L mol2 h2 ) observed rate constant of peracetic acid hydrolysis (L mol1 h1 ) thermodynamic dissociation constant of acetic acid concentration dissociation constant of acetic acid reaction temperature (K) charge number of ion B 3.1. Postulations of kinetic model Before developing the kinetic model, some proper postulations should be made to make the system easier. These postulations are as follows: (1) The volume of liquid reaction system keeps constant during reaction at a certain temperature. (2) The pKa value of AA at 298 K is 4.76 and does not change in the temperature span of 293323 K, and so is the pKa value of PAA. (3) The pKa value of PAA at 298 K is 8.2 [10], which is much larger than that of AA. Thus, the dissociation of PAA in acid condition can be negligible. (4) The thermal decomposition of HP and spontaneous decomposition of PAA in this temperature span can be also negligible. Actually, HP is very stable when no catalyst exists, even at a higher temperature. And thermal homolysis of PAA becomes obvious only at a higher temperature than 80 C [17]. Besides, there is much water existing in the system, and it is a stronger nucleophilic group than H2 O2 and CH3 COOH. Therefore, the consumption of PAA is mainly due to its hydrolysis. So the reactions in this system mainly consist of two reactions, synthesis and hydrolysis of PAA: CH3 COOH(A) + H2 O2 (B)
H2 SO4 ,k1 k2

Greek letters degree of dissociation of acetic acid activity coefcient

CH3 COOOH(C) + H2 O(D)

(3)

3.2. Development of kinetic model were given. The objective of this paper is to develop a kinetic model for PAA synthesis and hydrolysis in the presence of sulfuric acid in the liquid phase, the effects of ionic strength and H+ concentration being considered. The kinetic constants of forward and reverse reactions were obtained by tting the experimental data, and corresponding mathematical expressions for kinetic constants were given. 2. Experimental All the chemicals were analytically pure and purchased locally. Before the reaction, certain volumes of AA and SA were put in 100 ml clean ground-glass stoppered asks. Then certain volumes of 30% HP were added and mixed homogeneously. The initial volume ratio of AA and 30% HP was 1.5. The system was kept at a constant temperature in a water bath. Samples were taken and quickly analyzed in accordance with the Chinese Standard GB/T 19108-2003, which was the iodometric method. Each datum was the average result of at least double tests. Deioned water was used in all the experiments. The kinetic constants were obtained by tting experimental data by a simplex optimization method using MATLAB 6.5 software. According to Eq. (3), a homogenous kinetic model can be developed as follows: dCB = k2obs CC CD k1obs CA CB dt dCC = k1obs CA CB k2obs CC CD dt (4) (5)

where k1obs and k2obs are observed rate constants for forward and reverse reactions, respectively. As these reversible reactions are acid-catalyzed reactions, the observed rate constants must be the function of H+ concentration ([H+ ]). So, we can assume that k1obs and k2obs could be written as the following formulas: k1obs = k1 [H+ ] , k2obs = k2 [H+ ] , where k1 and k2 are intrinsic rate constants for the forward and reverse reactions. and are corresponding reaction orders. According to mass conservation, the concentrations of AA and water can be calculated with their initial concentrations and PAA concentration: CA = CA0 CC , CD = CD0 + CC . Thus, the kinetic equations can be written as: dCB = k2obs CC (CD0 + CC ) k1obs (CA0 CC )CB dt (6)

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dCC = k1obs (CA0 CC )CB k2obs CC (CD0 + CC ) dt

(7)

Table 1 Values of k1obs (L mol1 h1 ) at different temperatures with different H+ concentration H+ concentration (mol L1 ) T (K) 293 303 0.001040 0.002563 0.008575 0.016113 0.048969 313 0.001993 0.004991 0.018244 0.034500 0.083156 323 0.004113 0.008944 0.046263 0.079450 0.200563

In the system, H+ mainly comes from two parts, dissociation of sulfuric acid and AA, namely: [H+ ] = [H+ ]AcH + [H+ ]H2 SO4 The dissociation of AA is controlled by the equilibrium: CH3 COOH CH3 COO + H+ with Ka,AcH = aCH3 COO aH+ aCH3 COOH CH3 COO H+ = KC,AcH = 1.75 105 CH3 COOH (9) (8)

0.0018 0.0250 0.1250 0.2500 0.6250

0.000461 0.001356 0.003381 0.007725 0.021313

(10)

Table 2 Values of k2obs (L mol1 h1 ) at different temperatures with different H+ concentration H+ concentration (mol L1 ) T (K) 293 0.0018 0.0250 0.1250 0.2500 0.6250 0.000076 0.000746 0.001206 0.002863 0.007281 303 0.000309 0.001265 0.003238 0.006000 0.017250 313 0.000980 0.002040 0.007763 0.013538 0.029770 323 0.001855 0.003806 0.018613 0.032225 0.075750

where Ka,AcH and KC,AcH are thermodynamic dissociation constant and concentration dissociation constant of AA, respectively. a and are activity and activity coefcient, respectively, with their relation of a = C. The activity coefcient can be calculated by Davies formula: {I} ln = 1.171|z+ z | 0.30{I} (11) 1 + {I} where {I} denotes the value of ionic strength I. In our models, I was calculated approximatively from molar concentration of species:
1 1 I = 2 (bH+ + bCH3 COO + 4bSO2 )= 2 (2bCH3 COO + 6bSO2 )
4 4

= bCH3 COO + 3bSO2 CA + 3CSO2

(12)

where is the degree of dissociation of AA. So the H+ concentration can be obtained by the following expressions: [H ] =
+

2CSO4 2 +

(2CSO4 2 )2 + 4(CA0 CC )KC,AcH 2 (13)

or H+ concentration, k1obs and k2obs were both increased. It indicates the forward and reverse reactions are both acid-catalyzed processes, which is in accordance with the conclusions of some literatures [13,18]. The plots of k1obs versus [H+ ] and k2obs versus [H+ ] are shown in Fig. 3, and the linear tting results are summarized in Table 3. It has indicated a good linear relationship between k1obs and [H+ ] or k2obs and [H+ ], which shows that the synthesis and hydrolysis of PAA are both rst-order reactions with respect to H+ concentration. Similar results were also obtained according to Koubeks studies [15]. Table 3 also summarizes the intrinsic rate constants for the forward and reverse reactions estimated from the slopes of linear plots. So we can get the conclusion that the synthesis of PAA by the reaction of AA and HP is rst order

KC,AcH

1.75 105 exp{2.342[ (CA0 CC ) + 3CSO4 2 /(1 + (CA0 CC ) + 3CSO4 2 ) 0.30[(CA0 CC ) + 3CSO4 2 ]]}

(14)

It is clear that when the charge of sulfuric acid is too small, H+ from AA is not negligible. But when the charge of sulfuric acid is large enough, the H+ in the system can be thought being only from complete dissociation of sulfuric acid. 3.3. Determination of kinetic constants The comparison of calculated data and experimental data of PAA and HP concentrations versus time at several reaction temperatures are shown in Figs. 1 and 2. It is clear that the model well predicts the concentrations of PAA and HP during the reaction. The values of k1obs and k2obs determined by tting experimental data with our kinetic models are shown in Tables 1 and 2, respectively. We can see that with the increase in reaction temperature

with respect to AA concentration, HP concentration and as well as acid concentration. Similarly, the hydrolysis of PAA in acid
Table 3 Results of linear tting of k1obs vs. [H+ ] and k2obs vs. [H+ ] k1 (L mol2 h2 ) T (K) 293 R S.D. k2 (L mol2 h2 ) R S.D. 0.03347 0.99720 0.00064 0.01158 0.99636 0.00026 303 0.07621 0.99604 0.00177 0.02710 0.99704 0.00053 313 0.13423 0.99999 0.00153 0.04903 0.99869 0.00128 323 0.32219 0.99952 0.00357 0.12320 0.99930 0.00207

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Fig. 1. Experimental and calculated concentrations of PAA at several temperatures with different charge of sulfuric acid as catalyst: (a) T = 293 K; (b) T = 303 K; (c) T = 313 K; (d) T = 323 K. ( ) 0.00 mol L1 H2 SO4 ; ( ) 0.0125 mol L1 H2 SO4 ; ( ) 0.0626 mol L1 H2 SO4 ; ( ) 0.125 mol L1 H2 SO4 ; ( ) 0.3125 mol L1 H2 SO4 ;calculated values.

Fig. 2. Experimental and calculated concentrations of HP at several temperatures with different charge of sulfuric acid as catalyst: (a) T = 293 K; (b) T = 303 K; (c) T = 313 K; (d) T = 323 K. ( ) 0.00 mol L-1 H2 SO4 ; ( ) 0.0125 mol L-1 H2 SO4 ; ( ) 0.0626 mol L-1 H2 SO4 ; ( ) 0.125 mol L-1 H2 SO4 ; ( ) 0.3125 mol L-1 H2 SO4 ;calculated values.

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Fig. 4. The Arrhenius plots of the intrinsic rate constants and temperatures ( ) for k1 ; ( ) for k2 .

Therefore, the intrinsic reaction rate constants, k1 and k2 , at different temperatures (in Kelvin) can be calculated from the following expressions: k1 = 6.83 108 exp k2 = 6.73 108 exp 57846.15 RT 60407.78 RT (15) (16)

Fig. 3. Linear plots of k1obs vs. and k2obs vs. (a) k1obs vs. k2obs vs. [H+ ]. ( ) 293 K; ( ) 303 K; ( ) 313 K; ( ) 323 K.

[H+ ]

[H+ ]:

[H+ ];

(b)

Corresponding observed rate constants, k1obs and k2obs , follow the expressions as: k1obs = [H+ ] 6.83 108 exp 57846.15 RT 60407.78 RT (17) (18)

environment is rst order with respect to PAA concentration, water concentration and as well as acid concentration. Kunigk et al. found the decomposition of PAA was a rst-order reaction at 2545 C when the initial PAA concentrations were 240 and 280 mg L1 [16]. However, they did not mention the exact reaction mechanisms and the relationship between decomposition rate constants and H+ concentration. According to our results, we think that in this temperature range the decomposition of PAA referred to in their studies must be the hydrolysis process of PAA. The intrinsic activation energies of PAA synthesis and hydrolysis from the Arrhenius plots of data shown in Table 3 are 57.8 and 60.4 kJ mol1 , respectively (see Fig. 4), comparable with the decomposition activation energy of 66.2 kJ mol1 obtained in Kunigks studies [16]. An important aspect which should be noted is that the forward and reverse reactions have similar values of activation energy. It indicates the temperature affects the two reactions in similar degrees. However, the values of activation energy in our study are much larger than Dulnevas results (14.22 3.49 kJ mol1 for the forward reaction and 27.90 3.39 kJ mol1 for the reverse reaction) [13]. Their data were obtained in the presence of 0.057 M H2 SO4 in the system, so the activation energies must be observed activation energies, rather than intrinsic activation energies. This also proves that both of the forward and reverse reactions are acid-catalyzed processes.

k2obs = [H+ ] 6.73 108 exp 3.4. Reaction mechanisms

The mechanisms of PAA synthesis and hydrolysis have been proposed [13,18,19]. Using an 18 O isotope label, it was found that the reaction did not involve dissociation of the O O bond in initial hydrogen peroxide [20]. The hydrolysis of peroxyacids synthesized from HC18 OOH or CH3 C18 OOH and H2 O2 afforded hydrogen peroxide containing no heavy oxygen (18 O). This means that in both of the formation and hydrolysis of peroxyacids, the bond between the acyl group and oxygen atom is cleaved [13]. Rubio et al. studied the mechanism of formation of peracids taking the reaction between formic acid and hydrogen peroxide as a model for generation of performic acid. He proposed two different routes for the formation of performic acid, Route A and Route B. Route A consists of the addition of the hydrogen peroxide to the carbonyl carbon for the formation of a tetrahedral transitional state with the subsequent loss of a water molecule, while Route B is carried out in an acid medium for the activation of the carbonyl carbon and the subsequent addition of the hydrogen peroxide and the loss of a water molecule [19]. It is obvious that Route B is preferred, even on the occasion that no acid catalyst exits in the reaction system, because the organic acid (acetic acid or formic acid) can dissociate H+ , which can

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Fig. 5. Reaction mechanisms of PAA synthesis and hydrolysis with acid-catalysis: (a) PAA synthesis; (b) PAA hydrolysis.

further accelerate the reaction. So the forward and reverse processes may be described by the detailed schemes containing the moving of electrons, as shown in Fig. 5. However, as to the rate-determining step, different researchers gave different conclusions. Kharchuk et al. claimed that in acid-catalytic decomposition of peracetic acid, the controlling step was the protonation of PAA followed by the reaction of the active intermediate form [14]. Dulneva claimed that the rate-determining step in the forward reaction was elimination of water molecule from oxonium ion, and in the reverse reaction was the elimination of hydrogen peroxide [13]. Sawaki and Ogata claimed that the rate-determing step was the reaction between the actived carbonyl with hydrogen peroxide in the forward reaction or water in the reverse reaction [18]. However, Rubio et al. gave the conclusion that the determinant stage of the generation of peracids was the formation of the neutral tetrahedral intermediary [19]. In order to determine which step is the rate-determining step, we presume the synthesis of PAA follows the following three steps:

The rst step is the protonation of the carbonyl oxygen of acetic acid resulting in formation of an active intermediary E. A pre-equilibrium is employed for this step, which means the rate of formation of E and its decay back into reactants are much faster than its rate of formation of products, F and water. The step II is presumed to be the rate-determining step. The third step is also fast, namely k5 k4 , which implies the intermediary F can transform to peracetic acid very quickly. So we can obtain the rate of formation of PAA as: dCC dt
synthesis

dCF = k 4 CE CB dt

(22)

Since we assume that A, H+ and E are in equilibrium, we can write: k3+ [H+ ]CA = k3 CE Thus, the concentration of E can be expressed as: CE = k3+ + [H ]CA k3 (25) (23)

(19)

The rate of synthesis of PAA now may be written as: (20) dCC dt (21) =
synthesis

k4 k3+ + [H ]CA CB = k1 [H+ ]CA CB k3 (26)

= k1obs CA CB

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Analogously, the hydrolysis of PAA can be presumed to following the similar schemes:

57846.15 dCPAA = 6.83 108 exp dt RT [H+ ](CAA0 CPAA )CHP 6.73 108 60407.78 RT

(27)

exp

[H+ ]CPAA (CH2 O0 + CPAA )

dCHP 60407.78 = 6.73 108 exp dt RT (28) [H+ ]CPAA (CH2 O0 + CPAA ) 6.83 108 exp (29) The rate of hydrolysis of PAA similarly can be obtained: dCC dt =
hydrolysis

57846.15 RT

[H+ ](CAA0 CPAA )CHP

k7 k6+ + [H ]CC CD = k2 [H+ ]CC CD k6 (30)

= k2obs CC CD Thus, the rate of accumulation of PAA in the system is: dCC dCC = dt dt
synthesis

where CPAA and CHP are the concentrations of PAA and HP, and CAA0 and CH2 O0 are the initial concentrations of AA and water, respectively. It has been shown that the present kinetic equations can well describe our experimental data. It has been proved that the rate-determining step in synthesis of PAA is the reaction between H2 O2 with active carbonyl intermediary, and in the hydrolysis of PAA the reaction between water and corresponding active carbonyl intermediary. Acknowledgment

dCC dt

hydrolysis

= k1obs CA CB k2obs CC CD

(31)

The nancial support from Shell Global Solutions International is greatly appreciated. References
[1] L.B. Brasileiro, J.L. Colodette, D. Pilo-Veloso, Quim. Nova 24 (2001) 819829. [2] R. Gehr, M. Wagner, P. Veerasubramanian, P. Payment, Water Res. 37 (2003) 45734586. [3] M. Kitis, Environ. Int. 30 (2004) 4755. [4] Y. Cai, S.K. David, Text. Res. J. 67 (1997) 459464. [5] Z. Yuan, Y. Ni, A.R.P. Van Heiningen, Appita J. 51 (1998) 377380. [6] Q. Yang, F. Tang, Y. Zhang, China Pulp Pap. 22 (2003) 58. [7] P. Krizman, F. Kovac, F.T. Petra, Color. Technol. 121 (2005) 304309. [8] D.H. Stormont, Oil Gas J. 58 (1960) 7879. [9] R.L. Musante, R.J. Grau, M.A. Baltanas, Appl. Catal. A: Gen 197 (2000) 165173. [10] Z. Yuan, Y. Ni, A.R.P. Van Heiningen, Can. J. Chem. Eng. 75 (1997) 3741. [11] J.A. John, F.J. Weymouth, Chem. Ind. 2 (1962) 6269. [12] C. Wang, R. Fang, Chin. J. Disinf. 23 (2006) 100102. [13] L.V. Dulneva, A.V. Moskvin, Russ. J. Gen. Chem. 75 (2005) 11251130. [14] V.G. Kharchuk, L.A. Petrov, I.P. Kolenko, J. Appl. Chem. USSR 58 (1985) 12281232. [15] E. Koubek, The kinetics and the mechanism of the decomposition of aliphatic peroxyacids in aqueous solutions, Ph.D thesis, Brown University, New York, 1964. [16] L. Kunigk, D.R. Gomes, F. Forte, K.P. Vidal, L.F. Gomes, P.F. Sousa, Braz. J. Chem. Eng 18 (2001) 217220. [17] J.F. Kadla, H.-M. Chang, ACS Symp. Ser. 785 (2001) 108128. [18] Y. Sawaki, Y. Ogata, Bull. Chem. Soc. Jap. 38 (1965) 21032106. [19] M. Rubio, G. Ramrez-Galicia, L. Jovany L pez-Nava, J. Mol. Struc. o THEOCHEM 726 (2005) 261269. [20] C.A. Bunton, T.A. Lewis, D.L. Llewelyn, J. Am. Chem. Soc. 78 (1956) 1226.

This equation is actually our initial kinetic Eq. (5). Thus, the above presumed schemes are in accordance with our kinetic results. Therefore, it has been proved that the rate-determining step in the synthesis of PAA is the reaction between H2 O2 with active carbonyl intermediary, and in the hydrolysis of PAA the reaction between water and corresponding active carbonyl intermediary. Sawaki and Ogata also obtained the same conclusion [18]. 4. Conclusions A homogeneous kinetic model for peracetic acid (PAA) preparation from acetic acid (AA) and hydrogen peroxide (HP) was developed on the basis of some proper postulations. The synthesis and hydrolysis of PAA are both acid-catalyzed processes. The synthesis of PAA is rst-order with respect to AA concentration, HP concentration and H+ concentration. Similarly, the hydrolysis of PAA in acid environment is rst order with respect to PAA concentration, water concentration and H+ concentration. Linear relationships were found between the observed rate constants and H+ concentrations at a certain temperature, with the slopes being corresponding intrinsic rate constants. The intrinsic activation energies of PAA synthesis and hydrolysis from the corresponding Arrhenius plots are 57.8 and 60.4 kJ mol1 , respectively. Therefore, the kinetic equations for the preparation of PAA from AA and HP under the catalysis of sulfuric acid are as follows: