• Applied Chemistry for Engineering
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• v.17 no.3
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• pp.296-302
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• 2006

The kinetics of the thermal-oxidative decomposition of waste polyurethane (PU) according to oxygen concentration has been studied using a non-isothermal thermogravimetric technique at several heating rates from 10 to $50^{\circ}C/min$. A kinetic model accounting for the effects of the oxygen concentration by the differential and integral method based on Arrhenius equation was proposed to describe the thermal-oxidative decomposition of waste PU. To obtain the information on the kinetic parameters such as activation energy, reaction order, and pre-exponential factor, the thermogravimetric analysis curves and its derivatives have been analyzed using the kinetic analysis method proposed in this work. From this work, it was found that reaction orders for oxygen concentration had a negative sign, and activation energy decreased as the oxygen concentration increased. It was also found that the kinetic parameters obtained from the integral method using the single heating rate experiments varied with heating rates. Therefore, it is thought that the differential method using the multiple heating rate experiments more effectively represents the thermal-oxidative decomposition of waste polyurethane.

• Journal of Korean Society of Environmental Engineers
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• v.32 no.2
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• pp.219-226
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• 2010

In order to evaluate a removal characteristic of chloramphenicol, salicylic acid and ketoprofen according to dose of oxidants, $Cl_2$, $O_3$ and $O_3/H_2O_2$ are used as oxidants in this study. In case of that $Cl_2$ is used for oxidizing harmaceuticals, chloramphenicol, salicylic acid and ketoprofen is not removed entirely at $Cl_2$ dose rang of 0.5~5.0 mg/L for 60 min. However, removal tendency of salicylic acid is so obviously at $Cl_2$ dose higher than 1.0 mg/L. In addition, as $Cl_2$ dose and contact time increase, the removal rate of salicylic acid is enhanced. When $O_3$ is used as oxidant, chloramphenicol and ketoprofen is not eliminated at $O_3$ dose range of 0.2~2.0 mg/L. On the contrary, 30~70% of salicylic acid is removed at $O_3$ dose of 1.0~5.0 mg/L. Only 30% removal of salicylic acid is achieved at contact time of 5 min, however, the removal rate is enhanced remarkably at contact time over 10 min. In experiments using $O_3/H_2O_2$ as an oxidant, we can find that $O_3/H_2O_2$ is much more effective than $O_3$ only for removal of 3 pharmaceuticals, and the efficiency is raised according to increase of $H_2O_2$ dose. On reaction rate constant and half-life of 3 pharmaceuticals depending on $Cl_2$, $O_3$ and $O_3/H_2O_2$ dose, experiments using $O_3/H_2O_2$ show that oxidation of pharmaceuticals is less effective as the $H_2O_2/O_3$ ratio increases to above pproximately 1.0 related to reaction rate constant. An oxidation of salicylic acid by $Cl_2$ and $O_3$ particularly has a comparatively high reaction rate constant comparing $O_3/H_2O_2$, and thus salicylic acid is easily eliminated in oxidation processes.

• Journal of Korean Society of Environmental Engineers
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• v.31 no.10
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• pp.831-838
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• 2009

In order to evaluate a removal characteristic of diclofenac, ibuprofen and naproxen by oxidizing agents, $Cl_2,\;O_3$ and $O_3/H_2O_2$ are used as oxidants in this study. In case of that $Cl_2$ is used for oxidizing pharmaceuticals, ibuprofen is not removed entirely at $Cl_2$ dose range of 0.5~5.0 mg/L for 60 minutes, however, removal tendency of diclofenac and naproxen are so obviously at $Cl_2$ dose higher than 0.5 mg/L. In addition, as $Cl_2$ dose and contact time are increased, the removal rate of diclofenac and naproxen is enhanced. When $O_3$ is used as oxidizing agent, ibuprofen is not eliminated at $O_3$ dose range of 0.2~5.0 mg/L. On the contrary, 72~100% of diclofenac and 49~100% of naproxen are removed at $O_3$ dose of 0.2~5.0 mg/L. From experiments using $O_3/H_2O_2$ as an oxidant, we can find that $O_3/H_2O_2$ is much more effective than $O_3$ only for removal of diclofenac and naproxen. Moreover, the efficiency is raised according to increase of $H_2O_2$ dose, however, experiments using $O_3/H_2O_2$ show that oxidation of pharmaceuticals is less effective as $H_2O_2$ to $O_3$ ratio increased to above approximately 1.0. On reaction rate constant and half-life of diclofenac, ibuprofen and naproxen depending on $Cl_2$, $O_3$ and $O_3/H_2O_2$ dose, an oxidation of pharmaceuticals by $Cl_2$ and $O_3$ particularly has a comparatively high reaction rate constant and short half-life comparing $O_3/H_2O_2$. From above results, we can fine that diclofenac and naproxen can be easily eliminated in oxidation processes.

• Journal of Korean Society of Environmental Engineers
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• v.33 no.10
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• pp.723-730
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• 2011

In this experiment, persulfate, a strong oxidant for ISCO (In-Situ Chemical Oxidation) was used to degraded RDX in artificial ground water at ambient temperature. Results of RDX degradation by persulfate in a batch reactor showed that the oxidation reaction was pseudo first order with estimated Ea (activation energy) of $1.14{\times}10^2kJ/mol$ and the rate was increased with the increase of reaction temperature. The oxidation of RDX by persulfate increased slightly with the increase of initial solution pH from 4 to 8. The RDX oxidation rate increased 13 times at pH 10 compared with that at pH 4, however, alkaline hydrolysis was found to be the main reaction of RDX degradation rather than oxidation. The study also showed that the oxidation rate of RDX by persulfate was linearly dependent upon the molar ratios of persulfate to RDX from 5 : 1 up to 100 : 1, with a proportion constant of $4{\times}10^{-4}$ ($min^{-1}$/molar ratio) at $70^{\circ}C$. While NOM (Natural Organic Matter) exerted negative effects on the oxidation rate of RDX by persulfate, with a proportion constant of $1.21{\times}10^{-4}$ ($min^{-1}{\cdot}L/mg-NOM$) at $70^{\circ}C$ and persulfate/NOM molar ratio of 10/1. The decrease in RDX oxidation rate was linearly dependent upon the added NOM concentration. However, the estimated activation energy in the presence of 20 mg-NOM/L was within 3.3% error compared to that without NOM, which implies the addition of NOM does not alter intrinsic oxidation reaction.

• The Korean Journal of Food And Nutrition
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• v.13 no.4
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• pp.360-364
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• 2000

We studied the degree of rancidity of linoleic acid for the electrochemical redox reaction in time course and the kinetic parameters. The current of the linoleic acid was increased and the potential was shifted to the positive potential when scan rates were faster. The redox reaction of the linoleic acid was proceeding to totally irreversible and diffusion controlled reaction. From these results, diffusion coefficient(D$\_$o/) of linoleic acid was observed to 2.61$\times$10$\^$-6/ ㎠/s in the 0.1 M TEAP/DMF electrolyte solution. Also, exchange rate constant(K$\^$o/) was observed to 9.79$\times$10$\^$-11/ cm/s. The leaving time in air condition was found to affect the rancidity. We predicted that the product was carbonyl compounds.

• Korean Chemical Engineering Research
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• v.46 no.6
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• pp.1063-1068
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• 2008

The photocatalytic degradation of methylene blue water solution was carried out by irradiating microwave and UV light simultaneously using $TiO_2$ photocatalyst balls prepared by Chemical Vapor Deposition method. A microwave-discharged electrodeless UV lamp was developed to use microwave and UV simultaneously for photocatalytic reactions. The results of photocatalytic degradation of methylene blue showed that the decomposition rate increased with the microwave intensity, the circulating fluid velocity and auxiliary oxidizing agents added. Especially, the rate constant of $H_2O_2$-added photocatalytic reaction increased about three times from $0.0061min^{-1}$ to $0.0197min^{-1}$ when microwave was additionally irradiated. This study demonstrates that the microwave irradiation can play a very important role in photocatalytic degradation using peroxides although it is not easy to quantitatively assess the effect of microwave on photocatalytic reactions from the experimental data of this study.

• Resources Recycling
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• v.13 no.1
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• pp.28-38
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• 2004

The characteristics of cyanide decomposition in aqueous phase by electric oxidization have been explored in an effort to develop a process to recycle waste water. Considering current efficiency and voltage, the free cyanide decomposition experiment by electric oxidization indicated that 5 V of voltage and copper catalytic Cu/CN mole ratio 0.05 was the most appropriate condition, where current efficiency was 26%, and decomposition speed was 5.6 mM/min. High voltage and excess copper addition increased decomposition speed a little bit but not current efficiency. The experiment of free cyanide density change proves that high density cyanide is preferred because speed and current efficiency increase with density. Also, the overall decomposition reaction could be represented by the first order with respcect to cyanide with the rate constant of $1.6∼7.3${\times}$10^{-3}$ $min^{-1}$ The mass transfer coefficient of electric oxidization of cyanide came out as $2.42${\times}$10^{-5}$ $min^{-1}$ Furthermore, the Damkohler number was calculated as 5.7 in case of 7 V and it was found that the mass transfer stage was the rate determining step.

• Applied Chemistry for Engineering
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• v.8 no.3
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• pp.502-509
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• 1997

Aromatic pollutants(benzene, toluene, ethylbenzene and xylenes) were photodegraded by using a UV oxidation and the rates of degradation were investigated under various reaction conditions. Each of the solution containing 50 ppm benzene, 150 ppm ethylbenzene and 250 ppm xylenes was found UV-photodegraded over 90% in 1 hour of reaction time, wheras the only was 43 % degradation was obtained with 350 ppm toluene solution. A single component solution was more degradable than a mixed component solution and benzene was almost photodegraded at a pH 4.0, 6.4 and 10.0 after reaction time is 1 hr, ehtylbenzene was photodegraded about 92%(pH 4.0), 90%(pH 6.4) and 91%(pH 10.0), xylenes was photodegraded about 95%(pH 4.0), 90%(pH 6.4) and 92%(pH 10.0), but toluene was photodegraded about 80%(pH 4.0), 43%(pH 6.4) and 70%(pH 10.0), respectively. Kinetics studies show that the rate of decay in TOC(total organic carbon) were pseudo first-order rate except ethylbenzene, and then we could evaluate mineralization rate constants(k) of aromatics.

• Journal of Korean Society of Environmental Engineers
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• v.36 no.5
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• pp.311-316
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• 2014

Effects of operating parameters such as activated carbon dose and pH on the phenol oxidation in ozone-activated carbon hybrid process were investigated through a kinetic study. Activated carbon enhanced the self-decomposition of ozone, generating $OH{\cdot}$, thus promoting phenol degradation. The pseudo-first order rate constants of phenol degradation increased and half-life of phenol decreased with activated carbon dose. The increase of pH enhanced $OH{\cdot}$ generation through chain reactions initiated by $OH^-$, therefore increasing the phenol degradation rate. TOC removal efficiency increased about 3.2 times by adding activated carbon in ozonation process.

• Journal of the Korean Chemical Society
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• v.36 no.5
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• pp.644-651
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• 1992

The kinetics of the gas phase reaction of ozone(∼0.5 torr) with sulfur trioxide was investigated in the range of 6∼12 torr pressure at 69∼150${\circ}C$. The reaction rate of ozone with sulfur trioxide was faster than the reaction rate of $O_3 in the presence of CO_2 alone. No evidence for a molecular reaction of O_3 with SO_3 was found and the faster rate is probably due to impurity (HX) from the SO_3 reactant which gives rise to a chain reaction initiated by O_3 ＋ HX → OH ＋ O_2 ＋ X and also SO_3 has a larger collision diameter, which may be attributed to the O3 thermal decomposition more feasibly. The proposed experimental law [-d(O_3)/dt] = k_a(SO_3)(O_3) ＋ k_b(O_3)^{3/2} gives a rate constant ka(M-1 s-1) = (1.55 {\pm} 0.67) {\times} 105 e-{(9.27 0{\pm}0.43)kcal/RT}.$