• Environmental Analysis Health and Toxicology
• /
• 제12권3_4호
• /
• pp.1-13
• /
• 1997

First- and second-order kinetic oxidation rates of trichlorobenzenes (TCBs) were obtained and compared by a chemical activation system (CAS) which mimics mixed functional oxidase activity. The system consists of EDTA, ferrous sulfate, ascorbic acid, and $H_2O_2$ in potassium phosphdte buffer (monobasic at pH 7.4). The rate of transformation in CAS was enhanced in the presence and absence of catalase in the sequence 1, 2, 3-TCB < 1, 2, 4-TCB < 1, 3, 5-TCB. In general, the rates of degradation were greater in the test media with catalase. The effect of photolysis on the degradation of the TCBs with the CAS were examined. Sensitized photolysis with nitrite, Fenton's reagent, TiO$_2$ and triethylamine (TEA) studied in concert with the CAS demonstrated significant enhancement of the degradation rate of TCBs. Disappearance rates of TCBs in CAS with prior photolysis or prior photosensitization were at least 10-fold higher than the sum of the rate for each single experiment. This study proves that the combination of the CAS and photolysis can be used as a suitable technique for enhancing degradation of TCBs in aqueous systems.

• 한국재료학회지
• /
• 제26권8호
• /
• pp.406-411
• /
• 2016

In order to reuse the photocatalyst and enhance the photolysis efficiency, we have used atmospheric pressure dielectric barrier discharge (APDBD) to clean and activate $TiO_2$ powder. The photocatalytic activity of the $TiO_2$ powder before and after APDBD treatment was evaluated by the degradation of methylene blue (MB) in aqueous solution. The apparent reaction rate constant of photolysis of the first sample of reused $TiO_2$ cleaned by APDBD improved to a level up to 0.32h-1 higher than the 30 % value of the initial $TiO_2$ powder. As the number of photolysis reactions and APDBD cleanings increased, the apparent rate constants gradually decreased; however, the fourth photolysis reaction still showed a value that was greater than 10% of the initial value. In addition, APDBD treatment enhanced the process by which $TiO_2$ effectively adsorbed MB at every photolysis stage.

• 한국환경보건학회지
• /
• 제26권2호
• /
• pp.49-58
• /
• 2000

The present study was performed to investigate photodegradation rate constants and degradation products of phosphamidon and profenofos by the USEPA method. The two pesticides were very stable in 16 days exposure of sunlight from September 3 to 22, 1999 and humic acid had no sensitizing effect on the photolysis of each pesticide in sunlight. In the UV irradiation test, phosphamidon was rapidly degraded as increasing UV intensity. In case of UV irradiation with TiO2 and with TiO2 powder amount, degradation of profenofos showed no significant difference with UV irradiation. Photodegradation rate of profenofos was slower than that of phosphamidon. In order to identify photolysis products, the extracts of degradation products were analyzed by GC/MS. The mass spectra of photolysis products of phosphamidon were at m/z 153 and 149, those of the profenofos were at m/z 208 and 240, respectively. It was suggested that the photolysis products of phosphamidon were 0, 0-dimethyl phosphate(DMP) and N, N-diethylchloroacetamide, those of profenofos were 4-bromo-2-chlorophenol and 0-ethyl-S-propyl phosphate.

• 한국식품위생안전성학회지
• /
• 제14권4호
• /
• pp.339-345
• /
• 1999

Dichlorvos 및 methidathion에 대한 광분해 실험을 수행하여 속도상수와 분해생성물을 측정하였다. 햇빛을 이용한 광분해 실험은 1998년 9월 2일부터 9월 18일 까지 수행하였으며 두가지 농약이 상당기간 동안 안정함을 확인할 수 있었다. 또한 햇빛 아래서는 humic acid의 광관여 효과가 없음을 알 수 있었다. 자외선을 이용한 광분해 실험에서 dichlorvos의 광분해속도상수와 반감기는 각각 0.0208 및 33.3분으로 조사되었고, methidathion의 경우는 각각 0.6189 및 1.0분으로 조사되어 methidathion의 광분해는 4분 이내에 99% 이상의 매우 빠른 분해양상을 보였다. 두가지 농약 모두 3시간 이내에 분해되었고, 따라서 먹는물 정수처리시 농약의 분해가 필요할 때는 자외선을 이용하는 것이 좋을 것으로 생각된다. 또한, dichlorvos 및 methidathion은 자외선을 단독조사 하였을 때 보다 TiO$_2$를 첨가하였을 경우 분해는 다소 빠르게 진행되었다. 광분해에 의한 분해생성물을 확인하고자 GC/MS분석을 한 결과 dichlorvos에서는 분해생성물로 m/z=153의 Ο, Ο-dimethyl phosphate(DMP)를 확인하였다. Methidathion의 경우 분해생성물로 m/z=198 과 m/z=214로 각각 Ο, Ο-dimethyl phosphorothioate(DMTP)와 Ο, Ο-dimethyl phosphorodithioate(DMDTP)를 확인하였다.

• Journal of Photoscience
• /
• 제10권3호
• /
• pp.219-223
• /
• 2003

Phloxine B (2,4,5,7-tetrabromo-4,5,6,7-tetrachlorofluorescein disodium salt), also referred as D&C red dye no. 28, is phototoxic to many insects such as Tephritidae fruit flies. Sunlight photolysis of phloxine B in aqueous solutions was a first order kinetic reaction at low concentrations. But it turned to be more complex reactions with the increase of phloxine B concentration. The half-lives of phloxine B (6-120 ${\mu}$M) were 18-41 and 52-289 hours in oxygenated and deaerated distilled water, respectively. The photolysis rate constants increased as the phloxine B concentrations increased. The singlet oxygen formation positively correlated with the concentrations of phloxine B and humic acid in oxygenated distilled water. The formation of singlet oxygen did not stop even after the complete degradation of phloxine B, which suggested an involvement of photoproduct-mediated reactions. The results showed that singlet oxygen mediated photooxidation was a dominant reaction for phloxine B dissipation in an aqueous solution, and the self-sensitized and photoproduct-mediated reactions were also involved at the higher concentrations. Iodide and bromide ions significantly decreased phloxine B photolysis rate constants, which were in relation to the decrease of singlet oxygen formation.

• 한국식품위생안전성학회지
• /
• 제19권2호
• /
• pp.97-103
• /
• 2004

Piperophos에 대한 광분해 실험을 수행하여 속도상수와 분해생성물을 측정하였다. 햇빛을 이용한 광분해 실험은 2003년 10월 3일부터 10월 22일 까지 하였으며 상당기간 동안 농약이 햇빛에 안정함을 확인할 수 있었고, humic acid의 광관여 효과가 없음을 알 수 있었다. 자외선을 이용한 광분해 실험에서 piperophos는 자외선을 단독 조사하였을 때 자외선의 세기가 클수록 상대적으로 빠르게 분해되었으며, 광분해 촉매제인 TiO$_2$를 첨가하였을 경우에는 첨가하지 않고 자외선만 조사한 경우보다 상대적으로 느리게 분해되었다. 또, TiO$_2$의 양을 증가시켜도 별 차이가 없었다. 광분해에 의한 분해산물을 확인하고자 UMS분석을 한 결과 piperophos의 분해생성물은 m/z=166의 O,O-dipropyl phosphorodithioate로 추정된다.

• Journal of Photoscience
• /
• 제5권3호
• /
• pp.111-120
• /
• 1998

Sensitized photolysis of two onium borates (diphenyliodoium and dimethylphenacylsulfonium tetrakis(pentafluorophenyl)borate, 1a and 2a , respectively) and cationic photopolymerization of an epoxy monomer by the photolysis were investigate. The onium borates were sensitized by the excited singlet of the athracenes(non-substituted, 9-methyl-and 9, 10-dimethylanthracene) and generated acid by decomposing teemselves. The quantum yields of photobleaching of the anthracenes($\Phi$-AH) and acid generatiion (øacid) by the onium borates were the same order as those of the corresponding onium salts in aerated solutions (methanol and acetoitrile) and in argon(Ar) saturated acetonitrile. However, in the photolysis of the iodonium borates 1a in Ar saturated MeOH , øacid was much higher than the corresponding ø-AH. The acid generated by the photolysis of the onium borates initiated cationic polymerization of an epoxy monomer. The values of both rate of polymerization (Rp) and degree of conversion on the photopolymerization for the iodonium borated 1a were higher than those of the sulfoium borate 2a. In the photopolymerization for the iodonium borate 1a, both the Rp value and the degree of conversinio increased upon the addition of glycerol as a hydrogen donor. It is suggested that the increase of both values may be caused with the increase of øacid by addition of glycerol.

• 한국환경과학회지
• /
• 제13권1호
• /
• pp.37-40
• /
• 2004

In this study, the decomposition of gas-phase TCE, Benzene and Toluene, in air streams by direct UV Photolysis and UV/TiO$_2$ process was studied. For direct UV Photolysis, by regressing with computer calculation to the experimental results the value of reaction rate constant k of TCE, Toluene and Benzene in this work were determined to be 0.00392s$\^$-l/, 0.00230s$\^$-1/ and 0.00126s$\^$-1/, respectively. And the adsorption constant K of TCE, Toluene and Benzene in this work were determined to be 0.0519 mol$\^$-l/ ,0.0313mo1$\^$-1/ and 0.0084mo1$\^$-1/, respectively. For UV/TiO$_2$ system by regressing with computer calculation to the experimental results the value of reaction rate constant k of TCE, Toluene, and Benzene in this work were determined to be 5.74g/$\ell$$.$min, 3.85g/$\ell$$.$min, and 1.18g/$\ell$$.$min, respectively. And the catalyst adsorption constant K of TCE, Toluene, and Benzene in this work were determined to be 0.0005㎥/mg, 0.0043㎥/mg and 0.0048㎥/mg, respectively.

• 한국환경과학회지
• /
• 제11권10호
• /
• pp.1103-1108
• /
• 2002

In order to evaluate the degradation organophosphorus pesticide, EPN, in water environment, the effects of water temp.(10$^{circ}C,\;30^{\circ}C$), pH(3-11) and sunlight on its degradation were investigated during 10 days. The degradation rate of EPN(200 rpm) was faster at higher water temp. and higher pH, i.e., its degradation rate at pH 3, 5, 7, 9, 11 was 57, 63, 66, 69, 75%(1$0^{\circ}C$), and 70, 74, 79, 91, 97%(3$0^{\circ}C$) after 10 days, respectively. The effect of water temp. on its degradation was little in acidic condition, but was rather great in alkaline condition, with time. EPN was degraded fast at the alkaline condition by photolysis. At the condition of pH 11, EPN was degraded fast at the early stage in the first 2 days, but after that the degradation rate was weakened.

• 대한화학회지
• /
• 제10권1호
• /
• pp.43-45
• /
• 1966

The rate of exchange of I atom between alkyl iodides(ethyl or methyl iodide) and $I_2$ in n-hexane have been determined using $II^{131}$. It is found that the escape of $CH_3$ radicals from a solvent cage is faster than $C_2H_5$ radicals and that photolysis of $C_2H_5I$ is almost identical to that in the case of $CH_3I$.