Chemical Kinetics of Disproportionation Decomposition of tert-Butyl Hydroperoxide Catalyzed by Buserite-type Manganese Oxides

doi:10.15541/jim20150295

Abstract

Abstract:

The series of four buserite-type layered manganese oxides (Me-buserites) with different interlayer cations (Me, Me = Mg²⁺, Co²⁺, Ni²⁺, Cu²⁺) were synthesized by using both MnSO₄·H₂O as Mn source and K₂S₂O₈as oxidant. The as-synthesized Me-buserites were characterized by X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectrometry (ICP-AES) and N₂ adsorption-desorption (BET), in order to determine their crystal phases, elemental compositions and specific surface areas, respectively. In a 25 mL batch glass reactor, the disproportionation decomposition of tert-butyl hydroperoxide was kinetically investigated with the above Me-buserites as catalysts. The kinetic analyses show that the rate law established herein is second order in tert-butyl hydroperoxide, first order in Me-buserites and then third order overall, and that the apparent activation energy ranges from 56 kJ/mol to 125 kJ/mol. In accordance with the kinetic fittings, the proposed mechanism comprises two elementary reaction steps: pre-equilibrium step and rate-determining step. In terms of the pseudo-second-order rate constant and the half an hour-accumulated O₂ volume (both obtained at 338 K), the activity follows the order of Cu-buserite > Mg-buserite > Ni-buserite > Co-buserite. And a 100% selectivity towards tert-butyl alcohol is achieved over all the Me-buserites under selected reaction conditions.

Key words: buserite-type layered manganese oxides, tert-butyl hydroperoxide, tert-butyl alcohol, disproportionation decomposition, chemical kinetics

CLC Number:

O643

LU Shu-Pei, FENG Li-Li, QI Lin, WANG Li-Li, QI Xing-Yi. Chemical Kinetics of Disproportionation Decomposition of tert-Butyl Hydroperoxide Catalyzed by Buserite-type Manganese Oxides[J]. Journal of Inorganic Materials, 2016, 31(1): 14-20.

Figures/Tables 7

Fig. 1 XRD patterns of Na-birnessite and Me-buserites (a) Na-birnessite; (b) Mg-buserite; (c) Co-buserite; (d) Ni-buserite; (e) Cu-buserite

Table 1 Molecular formulas and BET surface areas of Me-buserites catalysts

Me-buserite	Molecular formula	S_BET / (m²·g^-1)
Mg-buserite	Na_0.03Mg_3.99Mn_14.00O_30.11·19.05H₂O	61
Co-buserite	Na_0.02Mg_3.29Co_0.54Mn_14.00O_29.54·19.56H₂O	63
Ni-buserite	Na_0.03Mg_1.32Ni_1.43Mn_14.00O_28.68·14.17H₂O	57
Cu-buserite	Na_0.03Mg_1.32Cu_3.40Mn_14.00O_31.23·16.43H₂O	56

Fig. 2 Two kinetic fittings of the Vt and V∞ data (catalyst: Cu-buserite) (a) the natural log fitting of ln[1/(V∞ - Vt)] versus t; (b) the linear fitting of 1/(V∞ - Vt) versus t. The line of (b) here is that of (b) in Fig. 3 and for the reaction conditions, also see those shown in Fig.3

Fig. 3 Plots of 1/(V∞ - Vt) versus t obtained with different [Cu-buserite]s Reaction conditions: T 338 K, TBHP (65wt% in H2O) 1.00 mL, [Cu-buserite]a 1.67 mg/mL, [Cu-buserite]b 3.33 mg/mL, [Cu- buserite]c 5.00 mg/mL, [Cu-buserite]d 8.33 mg/mL, acetonitrile 5.00 mL

Fig. 4 Plot of lnk’ versus ln[Cu-buserite]

Fig. 5 Arrhenius plot of lnk° ~ 1 / T Reaction conditions: Ta=323 K, Tb=328 K, Tc=333 K, Td=338 K, TBHP (65 wt% in H2O) 1.00 mL, [Cu-buserite] 8.33 mg/mL, acetonitrile 5.00 mL

Table 2 Kinetic parameters for disproportionation decomposition of TBHP catalyzed by Me-buserites and the O2 volume accumulated in a reaction period of 0.5 h

Me-buserite	α	β	E_a /(kJ·mol^-1)	k°/(mg^-1·mL·s^-1)^*	V_{0.5 h}/mL
Mg-buserite	2	1	89	8.19	41.7
Co-buserite	2	1	56	2.38	20.0
Ni-buserite	2	1	96	5.66	33.6
Cu-buserite	2	1	125	20.30	55.6

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