Pressure and temperature behavior of the cinnamaldehyde oxidation process was determined using a custom-designed mini closed pressure vessel test (MCPVT), which is a new method to investigate the stability and hazard assesment of the cinnamaldehyde oxidation reaction. The oxidation products were analyzed by gas chromatography-mass spectrometry (GC-MS). The results showed that cinnamaldehyde was stable under nitrogen atmosphere but very unstable under oxygen atmosphere. The initial oxidation products were analyzed by iodimetry and the cinnamaldehyde peroxide value could reach 139.44 mmol kg−1 when the oxidation temperature was 308 K. The oxidation kinetics of cinnamaldehyde were studied by using the pressure versus time (P–t) curves obtained from the MCPVT process. The reaction is a second-order reaction, the kinetic equation is ln k = −2233.66 × (1/T) + 11.19, and the activation energy Ea is 18.57 kJ mol−1 at 308–338 K. The explosion of the cinnamaldehyde oxidation reaction was observed by MCPVT, in which the onset temperature was 373 K. The main products of cinnamaldehyde oxidation are acetaldehyde, benzaldehyde, phenylacetaldehyde, acetophenone, 2-hydroxyphenyl acetone, cinnamaldehyde epoxide, benzoic acid, and cinnamic acid. Oxidation is a three-step process: (1) cinnamaldehyde reacts with oxygen to form peroxides; (2) complex oxidation reactions are caused by the thermal decomposition of peroxides; (3) rapid oxidation and thermal decomposition lead to explosion hazard.
The kinetics and thermodynamics of the adsorption process of reserpine adsorbed onto the strong acidic cationic exchange fiber (SACEF) were studied by batch adsorption experiments. The adsorption capacity strongly depended on pH values, and the optimum reserpine adsorption onto the SACEF occurred at pH = 5 of reserpine solution. With the increase of temperature and initial concentration, the adsorption capacity increased. The equilibrium was attained within 20 mins. The adsorption process could be better described by the pseudo-second-order model and the Freundlich isotherm model. The calculated activation energy Ea was 4.35 kJ/mol. And the thermodynamic parameters were: 4.97<ΔH<7.44 kJ/mol, -15.29<ΔG<-11.87 kJ/mol and 41.97<ΔS<47.35 J/mol·K. The thermodynamic parameters demonstrated that the adsorption was an endothermic, spontaneous and feasible process of physisorption within the temperature range between 283 K and 323 K and the initial concentration range between 100 mg/L and 300 mg/L. All the results showed that the SACEF had a good adsorption performance for the adsorption of reserpine from alcoholic solution.
Turpentine is a renewable resource, has good combustion performance, and is considered to be a fuel or promising additive to diesel fuel. This is very important for the investigation of thermal stability and energy oxidation characteristics, because evaluation of energy or fuel quality assurance and use safety are necessary. The main components of turpentine are α-pinene and β-pinene, which have unsaturated double bonds and high chemical activity. By investigating their thermal stability and oxidation reaction characteristics, we know the chemical thermal properties and thermal explosion hazard of turpentine. In this present study, the thermal stability and oxidation characteristics of α-pinene, β-pinene and α-pinene/β-pinene mixture were investigated using a high sensitivity accelerating rate calorimeter (ARC) and C80 calorimeter. The important parameters of oxidation reaction and thermal stability were obtained from the temperature, pressure and exothermic behavior in chemical reaction. The results show that α-pinene and β-pinene are thermally stable without chemical reaction under a nitrogen atmosphere even when the temperature reaches 473 K. The initial exothermic temperature of the two pinenes and their mixture is 333–338 K, and the heat release (−ΔH) of their oxidation is 2745–2973 J g−1. The oxidation activation energy (Ea) of α-pinene, β-pinene and α-pinene/β-pinene mixture is 116.25 kJ mol−1, 121.85 kJ mol−1, and 115.95 kJ mol−1, respectively. There are three steps in the oxidation of pinenes: the first is the induction period of the oxidation reaction; the second is the main oxidation stage, and the pressure is reduced; the third is thermal decomposition to produce gas.
The thermal oxidation reaction process and oxidation kinetics of abietic acid were investigated by using self-designed gas–solid reaction equipment. The oxidation product and intermediates of the oxidation reaction of abietic acid were tracked by LC-MS. The results revealed a two-step oxidation reaction of abietic acid: abietic acid forms a peroxide first, followed by cracking to form hydroxyl-containing oxidized abietic acid. Both of the steps followed the pseudo-first order reaction kinetics, in which the kinetic equation of the first step is r1 = cA × 3.51 × 103 × exp(−58.96 × 103/RT), with activation energy of 58.96 kJ mol−1. The kinetic equation of the second step is r2 = cO × 6.09 × 105 × exp(−48.06 × 103/RT) with activation energy of 48.06 kJ mol−1. The kinetic equation of the total reaction is ra = ca × 1.12 × 106 × exp(49.51 × 103/RT) with apparent activation energy of 49.51 kJ mol−1.