• Title/Summary/Keyword: photolysis

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Vacuum Ultraviolet Photolysis of Ethyl Bromide at 123.6 nm

  • Hee-Soo Yoo;K. H. Jung
    • Bulletin of the Korean Chemical Society
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    • v.1 no.1
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    • pp.35-39
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    • 1980
  • A vacuum ultraviolet photolysis of ethyl bromide was studied in the pressure range of 0.5-19.9 torr and at 123.6 nm krypton resonance line. The pressure effect on the reaction was studied by increasing the reactant pressure and by adding an inert gas, e.g., He. In the observation the monatomic gas is found to be no effect in the reaction. A scavenger effect of the reaction was also performed by adding NO gas as a radical scavenger and was found to be quite efficient to scavenge a radical product $C_2H_6$. The observation of the major reaction product $C_2H_6$ was interpreted in terms of a molecular elimination. Nontheless the decreasing phenomenon of ${\phi}_{C_2H_4}/{\phi}_{C_2H_6}$ with pressure rise was attributed to the existence of the two electronically excited states. One state proceeds to the molecular elimination and the other to carbon-bromine bond fission. The excitation and the decomposition mechanisms between two excited states and the reaction products were interpreted in terms of the first excitation which proceeds the molecular elimination, and the second excitation which resulted from the first excited state by collisional cross over decomposes by carbon-bromine bond fission.

Depletion Kinetics of Ground State FeO Molecules by $O_2, N_2O, and \;N_2$

  • Son, H. S.
    • Bulletin of the Korean Chemical Society
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    • v.21 no.6
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    • pp.583-587
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    • 2000
  • Depletion kinetics of ground state FeO molecules by $0_2$, $N_2O$ and $N_2$ has been studied at room temperature. The ground state FeO molecules were generated by photolysis of a $Fe$(CO)_5$/M(O_2$, $N_2O)/He$ mixture using an unfocused weak UV laser beam. The formation of ground state FeO molecules was identified by a laser-induced fluorescence (LIF) method. The intensity distribution of those undisturbed rotational lines suggests that the rotational temperature of the ground state FeO molecules is lower than room temperature. The LIF intensities of FeO molecules at different partial pressures of $0_2$, $N_2O$ and $N_2$ were monitored as a function of the time delay between the photolysis and probe laser pulses to obtain the depletion rate constants for the ground state FeO. They were 1.7+ 0.2x $10^{-12}$, 4.8 $\pm0.4$ x $10^{-12}$, and $1.4\pm$ 0.2x $10^{-12}cm^3$molecule^{-1}s^{-1}$$ by $0_2$, $N_20$, and $N_2$, respectively.

Diminution of Pesticide Residues on Crops and Soil by Accelerated Photolysis (광분해(光分解) 촉진(促進)에 의한 작물(作物) 및 토양중(土壤中) 농약잔유물(農藥殘留物)의 경감(輕減)에 관한 연구(硏究))

  • Lee, Jae-Koo;Jung, In-Sang;Kwon, Jeong-Wook;Ahn, Ki-Chang
    • Korean Journal of Environmental Agriculture
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    • v.17 no.2
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    • pp.107-116
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    • 1998
  • In an effort to reduce artifically the residual pesticides on crop and soil by accelerated photolysis,some 40 among the naturally occurring and synthetic coumpound were screened for photosensitization and/or photocatalysis and six promising chemicals were selected.The fungicides and the four selected photosensitizers and/or photocatalyst (PS) were applied to each crop.The results obtained are summarized as follows. 1. The wavelengths of maximum absortion (${\lambda}$max) and the molar absorptivites (${\varepsilon}$max) of procymidone,vinclozolin,and carbendazim in acentone were all 209 nm and 853,854,and 8740 respectively. 2. Of the 40 naturally-occuring and synthetic compounds screened,six promising ones were selected and designated as PS-1 (aromatic ketone),PS-2(aromatic amine)PS-3(quinone) ,PS-4 (inorganic compound),PS-5(organic acid salt) and PS-6(semiconductor photocatalyst). 3. In the accelerated photolysis of pesticide in soil by applying PS ,procymidone was decoposed rapidly by virtue of PS-2,being 59% of the control 3 days after application. 4. The vinclozolin residue in soil was reduced to 71% and 21% of the control 1 and 15 days,respectively,after PS-2 application. 5. The photolysis of carbendazim in soil was not accelerated by any of the PS tested. 6. The pesticide residues on the crop were prominently reduced by PS application.The procymidone residue on tomato was reduced to 47% of the control 15 days after PS-1 application and that on red pepper reduced to 57% 15 days after PS-2 application. 7. Vincrozolin residus remaining on tomato 1 and 15 days after PS-2 application were 38% and 56% of the control whereas those on the red pepper were 82% and 64%,respectively. 8. PS-2 was the most effective for the accelerated photolysis of carbendazim residues remaining on tomato, whereas on red pepper, the four of PS tested were all effective, but did not make much difference between them. This might be due to the shielding of sunlight by the leaves of red pepper not to exert the photosensitizing effect of PS-2 to the full.

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Photolysis of the insecticide imidacloprid in water and water-paddy soil systems (살충제 imidacloprid의 물 및 물-토양계 중 광분해)

  • Ihm, Yang-Bin;Kyung, Kee-Sung;Kim, Chan-Sub;Choi, Byeong-Ryeol;Hong, Soo-Myung;Lee, Jae-Koo
    • The Korean Journal of Pesticide Science
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    • v.8 no.1
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    • pp.38-45
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    • 2004
  • To elucidate the photolysis characteristics of the insecticide imidacloprid in the environment, $[^{14}C]$imidacloprid was treated into water and paddy soil-water system. In water system, the amount of $^{14}C$-radioactivity distributed in aqueous phase was rapidly increased up to 80% of total $^{14}C$ in water during 7 days of exposure to sunlight. Also, the amounts of imidacloprid in water at day 0 and 3 days after treatment were 1.2461 and 0.8594 mg/kg, respectively, not being detected 7 days after treatment, indicating rapid degradation of imidacloprid in water by sunlight. One photodegradation product, imidacloprid urea, in which the $N-NO_2$ moiety of imidacloprid was replaced by oxygen, was detected from water in water and water-paddy systems. The amount of the metabolite detected from water in water system was 0.0112 mg/kg 1 day after treatment and reached the top concentration of 0.0391 mg/kg 7 days after treatment. In case of water-paddy system, its amount was 0.0117 mg/kg 1 day after treatment and reached the highest concentration of 0.0259 mg/kg 3 days after treatment. Rapid transformation of imidacloprid into polar compounds continued until 7 days after treatment, considering that 80% of $^{14}C$ in water distributed in aqueous phase 7 days after treatment, amount of imidacloprid was 1.6538 mg/kg at day 0 and 0.8785 mg/kg 1 day after treatment, not being detected after 15 days, indicating rapid degradation of imidacloprid in water-paddy soil system by sunlight. The direct degradation of imidacloprid to imidacloprid urea would be a major photodegradation pathway in water and water-paddy soil systems.

Effect of Ni Addition on ATiO3 (A = Ca, Sr, Ba) Perovskite Photocatalyst for Hydrogen Production from Methanol Photolysis (메탄올 광분해 수소제조를 위한 ATiO3 (A = Ca, Sr, Ba) Perovskite 광촉매의 Ni 첨가 영향)

  • Kwak, Byeong Sub;Park, No-Kuk;Lee, Tae Jin;Lee, Sang Tae;Kang, Misook
    • Clean Technology
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    • v.23 no.1
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    • pp.95-103
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    • 2017
  • In this study, $ATiO_3$ (A = Ca, Sr, Ba) perovskite, which is the widely known for non $TiO_2$ photocatalysts, were synthesized using sol-gel method. And Ni was added at the A site of $ATiO_3$ by using that it is easy to incorporate. The physicochemical characteristics of the obtained $ATiO_3$ and Ni-$ATiO_3$ particles were confirmed using the X-ray diffraction (XRD) UV-visible spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), the $N_2$ adsorption-desorption isotherm measurement, and X-ray photoelectron spectroscopy (XPS). The $H_2$ was produced using the photolysis of MeOH. Using the Ni-$ATiO_3$ photocatalysts, $H_2$ production was higher than using the $ATiO_3$ photocatalysts. Especially, $273.84mmolg^{-1}$ $H_2$ was produced after 24 h reaction over the Ni-$SrTiO_3$. Also in the water (0.1 M KOH) with the Ni-$SrTiO_3$, $H_2$ production was $961.51mmolg^{-1}$ after 24 h reaction.

Persistence and degradation of herbicide molinate in paddy-soil environment (논토양 환경 중 제초제 molinate의 잔류성과 분해특성)

  • Park, Byung-Jun;Park, Hyeon-Ju;Lee, Byung-Moo;Ihm, Yang-Bin;Choi, Ju-Hyeon;Ryu, Gab-Hee
    • The Korean Journal of Pesticide Science
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    • v.9 no.1
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    • pp.60-69
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    • 2005
  • The herbicide molinate has been detected with high frequency in the main river during the growing season in Korea. To elucidate the exposure of molinate in agricultural environment, the persistence and the degradation characteristics of molinate were investigated in paddy ecosystems. The half-lives of molinate were 4.1 days with soil aquatic system, and 4.2 days in only aquatic system. Initial dissipation rate of molinate in water was greater with soil aquatic system than that of only aquatic system. Photolysis of molinate was occurred about 31.0% of molinate treated in pure water, when irradiated at 5,530 $J/cm^2$ by the xenon lamp, but its hydrolysis was stable. For the accelerated photolysis of molinate in aqueous solution, several photosensitizers were screened, showing that the hydroperoxide($H_2O_2$) and acetone were prominent among the chemical tested. When hydroperoxide and zinkoxide(ZnO) were used as photosensitizer, their photolysis were accelerated greater than 98% and 58% in aqueous solution, respectively. Elution rate of molinate as granular formulations in aqueous system was more than 90% in 30 hour at $35^{\circ}C$. Molinate concentration pattern in paddy water was rapidly decrease from treatment till 7 days in paddy rice field and its half-lives were 3.7 days($Y=1.9258{\times}e^{-0.1865X}$(r=-0.9402)).

Time Resolved ESR Studies on Short-Lived Reaction Intermediates Produced by Laser Photolysis of Anthraquinone in Organic Solvents (유기용매에서 Anthraquinone의 광반응에서 생성하는 짧은 수명의 반응중간체에 관한 시간분해 ESR 연구)

  • Hong, Daeil;Yun, Young Hyoun;Sohn, Moo-Jeong;Kim, Kyung-Chan;Kuwata, Keiji
    • Journal of the Korean Chemical Society
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    • v.39 no.4
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    • pp.237-243
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    • 1995
  • The measurments of neutral semiquinone radicals, which were formed from the laser flash photolysis of anthraquinone (AQ) in the mixed solvents were carried out by the time resolved electron spin resonance (trESR) spectroscopy. The chemically induced dynamic electron polarization (CIDEP) spectra of the neutral semiquinone radical (AQH${\cdot}$) and semiquinone radical anion (AQ${\cdot}$-) were successively detected in the laser flash photolysis of AQ in the mixtures of 2-propanol (PrOH) and triethylamine (TEA). The neutral semiquinone radical was short-lived with the half-life of 0.8 ${\mu}sec$, whereas the semiquinone radical anion was relatively stable and then its cwESR could be observed. The rate constant of the spin-depolarization of semiquinone radical anion was $2.6{\times}10^5 sec^{-1}$ and the decay of the radical anion was the first order reaction with the rate constant of $3.0{\times}10^2\; sec^{-1}$. No CIDEP of semiquinone radical anion was observed in the mixture of PrOH and the lower concentration of TEA than 2 percent. The CIDEP spectrum of the neutral semiquinone radical was detected in the mixture of benzene and TEA with the half-life of 3.0 ${\mu}sec$. The neutral semiquinone radical could not be detected by cwESR. Neither CIDEP nor ESR absorption could be observed in PrOH, TEA or benzene only.

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The Study of Statistical Optimization of MTBE Removal by Photolysis(UV/H2O2) (광분해반응을 통한 MTBE 제거에 대한 통계적 최적화 연구)

  • Chun, Sukyoung;Chang, Soonwoong
    • Journal of the Korean GEO-environmental Society
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    • v.12 no.9
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    • pp.55-61
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    • 2011
  • This study investigate the use of ultraviolet(UV) light with hydrogen peroxide($H_2O_2$) for Methyl Tert Butyl Ether(MTBE) degradation in photolysis reactor. The process in general demands the generation of OH radicals in solution at the presence of UV light. These radicals can then attack the MTBE molecule and it is finally destroyed or converted into a simple harmless compound. The MTBE removal by photolysis were mathematically described as the independent variables such as irradiation intensity, initial concentration of MTBE and $H_2O_2$/MTBE ratio, and these were modeled by the use of response surface methodology(RSM). These experiments were carried out as a Box-Behnken Design(BBD) consisting of 15 experiments. Regression analysis term of Analysis of Variance(ANOVA) shows significantly p-value(p<0.05) and high coefficients for determination values($R^2$=94.60%) that allow satisfactory prediction of second-order regression model. And Canonical analysis yields the stationery point for response, with the estimate ridge of maximum responses and optimal conditions for Y(MTBE removal efficiency, %) are $x_1$=25.75 W of irradiation intensity, $x_2$=7.69 mg/L of MTBE concentration and $x_3$=11.04 of $H_2O_2$/MTBE molecular ratio, respectively. This study clearly shows that RSM is available tool for optimizing the operating conditions to maximize MTBE removal.

Silyl-Tranfer Photoreactions of Trimethylsilylmethyl Substituted Acyclic N-Sulfonylbenzamides

  • Oh, Sun-Wha
    • Journal of Photoscience
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    • v.12 no.2
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    • pp.63-66
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    • 2005
  • The azomethine ylide forming photoreaction has been explored by probing the excited state chemistry of several N-trimethylsilylmethyl substituted cyclic and acyclic imides and amide analogs. N-[(Trimethylsilyl)methyl]-N-mesylbenzamide (5) undergoes the excited state C to O silyl migration reaction to produce azomethine ylide intermediate 13. This ylide undergoes electrocyclization to form transient aziridine intermediate 14 which react further by ring opening to generate N-phenacylamine product 10. On the other hand, photolysis of N-[N-mesyl-N-(trimethylsilyl)methyl]aminoethyl-N-mesylbenzamide (8) brings about desilylation resulting in the production of dimer 17.

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A Study on the Photodegradative Behavior of the Dibenzothiophene (DBP) in Water System (수용액중의 디벤조치오펜의 광화학적 분해반응의 연구)

  • Kim, Jae-Hyoun
    • Environmental Analysis Health and Toxicology
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    • v.14 no.3
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    • pp.121-126
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    • 1999
  • The present paper describes a study of the photochemical kinetics and its oxidation mechanism of DBT. The photolysis of DBT in aqueous solution media have shown to have significant oxidation activities for the photolytic desulfurization of DBT. The oxidation effect was more pronounced in 4 % NaCl solution. A mechanism was proposed that the desulfurization process arise from the substution of sulfur by the hydroxyl radicals in different aqueous medium.

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