• Title/Summary/Keyword: Photochemical Reaction Mechanism

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Numerical Study on the Process Analysis of Ozone Production due to Emissions Reduction over the Seoul Metropolitan Area (수도권 배출량 저감에 따른 오존 발생 과정 분석에 관한 수치연구)

  • Jeong, Yeo-Min;Lee, Soon-Hwan;Lee, Hwa-Woon;Jeon, Won-Bae
    • Journal of Environmental Science International
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    • v.21 no.3
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    • pp.339-349
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    • 2012
  • In order to clarify the impact of emissions reductions on the air quality over Metropolitan area of Korean Peninsula, several numerical experiment and analysis of integrated process rate(IPR) of ozone were carried out. Numerical models used in this study are WRF for the estimate the meteorological elements and CMAQ for assessment of ozone concentration. As result in the sensitive test of VOC/NOx reduction experiments, although VOC reduction tends to induce the different impact on the advection and photochemical reaction rate of ozone in urban area and rural area, the mechanism of ozone appeared to be more sensitive to the reduction of VOC than that of NOx over the metropolitan and its surround area. So the control of VOC emission inventories is an effective means to decrease the ozone concentrations around this area.

Photochemistry of Benzanilide I Photocyclization of Benzanilides (벤즈아닐리드류의 광화학 (제1보). 벤즈아닐리드류의 광고리화 반응)

  • Yong-Tae Park;Sang-Rok Do;Kap-Duk Lee
    • Journal of the Korean Chemical Society
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    • v.29 no.4
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    • pp.426-436
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    • 1985
  • Preparative and kinetic photochemical reactions of several benzanilides were studied. Several substituted benzanilides were synthesized by acylation of substituted anilines with substituted benzoyl chlorides. While benzanilide gave a photo-Fries type reaction product, 2-chlorobenzaniline, 2-bromobenzanilide, and 2-methoxybenzanilide gave a photocyclization reaction product, phenanthridone. Since 8-chlorophenanthridone was obtained from 2,2'-dichlorobenzanilide, the carbonyl phenyl is the excited site. Quantum yield of photocyclization of 2-chlorobenzanilide, 2'-chlorobenzanilide, and 2-methoxybenzanilide were obtained. 2-Chlorobenzanilide was photocyclized effectively and 2'-chlorobenzanilide ineffectively. Since the oxygen present in the reaction medium retarded the photocyclization reaction of 2-chlorobenzanilide, the triplet state of 2-chlorobenzanilide is involved. The mechanism of the photocyclization of 2-chlorobenzanilide is suggested: $\pi-complex$ between carbonyl phenyl and N-phenyl was formed from the triplet state of 2-chlorobenzanilide; neighbour phenyl (N-phenyl) assists for leaving of chlorine from carbonyl phenyl to make an intermediate, cyclized conjugated radical, because electron donating group on the N-phenyl ring accelerated the reaction; hydrogen detachment from the intermediate is obviously not a rate determined step because there was no isotope effect on the rate of photocyclization. The photocyclization reaction rate of 2-methoxybenzanilide was faster in the presence of oxygen than in the absence of oxygen. Thus, the singlet excited state of 2-methoxybenzanilide is involved in the reaction. Probably, the intermediate, methoxyhydro-phenanthridone is oxidized by oxygen in the medium to give phenanthridone.

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Mechanism of Orientation of Liquid Crystal Molecules for Polarized UV-exposed Polyimide Alignment Layers (폴리애미드 배향막의 편광 자외선 조사에 따른 액정 배향 메카니즘)

  • 김일형;김욱수;하기룡
    • Polymer(Korea)
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    • v.26 no.2
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    • pp.209-217
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    • 2002
  • We studied the mechanism of orientation of polyimide molecules which were irradiated by polarized UU (PUV) using polarized Fourier transform infrared (FT-IR) spectroscopy and ultraviolet (UV) spectroscopy, According to the measured UV spectra, we found PI films mainly absorb UV light less than 350 nm wavelength, therefore, UV light less than 360 nm induces photochemical reaction of PI. PUV irradiation of PI films caused decrease of all peak intensities in the FT-IR spectra. except the newly formed broad peak at $3244 cm^{-1}$, due to degradation of the PI molecules. The remaining PI molecules after photo-degradation showed predominantly perpendicular molecular orientation to the irradiated PUV polarization direction, due to the preferential degradation of PI molecules parallel to irradiated PUV polarization direction. However the rubbing of PI films induced reorientation of the PI molecules parallel to the rubbing direction. We also investigated the alignment of the liquid crystal by rubbing or PUV irradiation. Liquid crystals align perpendicular to the PUV polarization direction and parallel to the rubbing direction.

Development of a Short-term Model for Ozone Using OPI (오존최대농도지표를 이용한 오존단기예측모형 개발)

  • 전의찬;김정욱
    • Journal of Korean Society for Atmospheric Environment
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    • v.15 no.5
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    • pp.545-554
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    • 1999
  • We would like to develop a short-term model to predict the time-related concentration of ozone whose reaction mechanism is complex. The paper targets Seoul where an ozone alert system has recently been employed. In order to develop a short-term prediction model for ozone, we suggested the Ozone Peak Indicator(OPI), an equivalent of the potential daily maximum ozone concentration, with precursors being the only limiting factor, and we calculated the Ozone Peak Indicarot as OPI={$ rac{(O_3)_{max}cdot(H_{eH})_{max}(Rad)_{max}$ to preclude the influence of mixing height and solar radiation on the daily maximum ozone concentration. The OPI on the day of the prediction is to be calcultated by using the relation between OPI and the initial value of precursors. The basic prediction formula for time-related ozone concentration was established as $O_3(1)={(OPI)cdot Rad(t-2)H_{eH}}$, using the OPI, solar radiation two hours before prediction and mixing height. We developed, along with the basic formula for predicting photochemical oxidants, "SEOM"(Seoul Empirical Oxidants Model), a Fortran program that helps predict solar radiation and mixing height needed in the prediction of ozone pollution. When this model was applied to Seoul and an analysis of the correlation between the observed and the predicted ozone concentrations was made through SEOM, there appeared a very high correlation, with a coefficient of 0.815. SEOM can be described as a short-term prediction model for ozone concentration in large cities that takes into account the initial values of precursors, and changes in solar radiation and mixing height. SEOM can reflect the local characteristics of a particular and region can yield relatively good prediction results by a simple data input process.t process.

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Effects of NaOH and Humic Acid on the UV Photolysis of PCBs (PCBs의 광화학적 연구: NaOH 및 휴믹산 (humic acid, HA)에 의한 분해특성)

  • Shin, Hae Seung;Kim, Jae Hyoun
    • Journal of Environmental Health Sciences
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    • v.40 no.2
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    • pp.147-156
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    • 2014
  • Objectives: This study was carried out to examine whether the apparent photolysis with or without sensitizers [NaOH and humic acid (HA)] was prompted photodegradation of polychlorinated biphenyl (PCB) in aqueous solution. Methods: PCBs photodegradation occurred using fluorescence black lamps at ${\lambda}_{max}=300nm$. PCB congeners were exposed in 10 ppm HA or 0.05N NaOH solutions, to investigate the decreasing profile of PCB concentration with time. The PCBs were then analyzed by gas chromatography/mass spectrometry (GC-MS). Reductive degradation profile of PCB congeners in the presence of both sensitizers under oxygen-saturated protic conditions was described using the wind-rose diagrams. Results: Use of HA or NaOH decreased PCB concentration with time in the dark and on irradiation, indicating that photolysis underwent through reductive dechlorination through energy transfer and possibly with reactive oxygens. The dechlorination was marked by a chromatographic shift, observed in the GC-MS plots. Therefore it is logical to assume that increasing the dose of sensitizers would increase the photodegradation rates of PCBs. The half-lives of pentachloro-PCB (penta-3) in 0.05N NaOH and 10 ppm HA were estimated at about 47 hours and 39 hours, respectively, under the same experimental conditions of photolysis. It was found that the rate of photolysis of pentachloro-PCB in aqueous solution followed apparent first-order kinetics compared to other congeners. Conclusion: Photochemical degradation (using 328 nm UV light) of penta- and hexa-PCBs in HA or alkaline solution is a viable method for pretreatment method. The results are helpful for the further comprehension of the reaction mechanism for photolytic dechlorination of PCBs in aquatic system.

A STUDY ON A COMPARISON BETWEEN IN-VIVO AND IN-VITRO PHOTOTOXICITY TEST (IN-VIVO와 IN-VITRO에서의 광독성 시험법의 비교에 대한 연구)

  • Lee, Ho;Koh, Jae-Sook;Park, Won-Jae
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.19 no.1
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    • pp.57-76
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    • 1993
  • Phototoxicity is a complex phenomenon which may involve photochemical reaction and biological response mechanism. This complexicity and iii mal protecting tendency has led to the development of various in-vitro approaches as sensitive, alternative test to the in-vivo phototoxicity test. In this study, we investigated not only the sensitivity of two microorganism, (C. albicans and 5. typhimurium TA 98 about UV) but also a correlation between in-vitro and in-vivo phototoxicity test using UV A and 1 Furthermore, we studied the effect of irradiation method which were as follows 1) irradiate to material and microorganism, simultaneously 2) irradiate to only material 3) irradiate to material and microorganism, respectively In each irradiation method, it showed no significant difference, However we were able to observe the more sensitive phototoxicity in S. typhimurium TA 98 than C. albicans, and the results of in-vitro test using 5. typhimurium TA 98 had a good correlation with those of in-vivo test.

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The Mechanism of the Photocyclization of N-(2-Haloarylmethyl)Pyridinium and N-(arylmethyl)-2-Halopyridinium Salts

  • Yong-Tae Park;Chang-Han Joo;Chung-Do Choi;Kum-Soo Park
    • Bulletin of the Korean Chemical Society
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    • v.12 no.2
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    • pp.163-169
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    • 1991
  • The photochemical and photophysical properties of N-(2-haloarylmethyl)pyridinium, N-(arylmethyl)-2-halopyridinium, N-(2-haloarylmethyl)-2-halopyridinium salts and N-(2-halobenzyl)-isoquinolinium salt are studied. The pyridinium salts photocyclize to afford isoindolium salts, while the isoquinolium salts do not. In the photocyclization of N-(2-chlorobenzyl)-2-chloropyridinium salts, pyrido[2,1-a]-4-chloroisoindolium salt is formed by the cleavage of chlorine of pyridinium ring. This indicates that the excited moiety is not the phenyl ring, but the pyridinium ring. The triplet states of the pyridinium salts are believed to be largely involved in the photocyclization, since oxygen retards most of the reaction. Some assistance of a ${\pi}$-complex between the excited chlorine moiety of the salt and phenyl plane of the same molecule is required to explain the reactivity of the salts. N-(Benzyl)-2-chloropyridinium salt is two times more reactive than N-(2-chlorobenzyl)pyridinium salt. N-(Benzyl)-2-chloropyridinium salt can form ${\pi}-complex$ effectively because of the electron-rich phenyl group. The ${\pi}$-complex affords an intermediate, phenyl radical by cleaving the chlorine atom. The photocyclized product, isoindolium salt is obtained by losing the hydrogen atom from the phenyl radical. The reactive pyridinium salts 1a, 2a and 3a have a low fluorescence quantum yield (${\Phi}F$ < 0.01) and a higher triplet energy (ET > 68 kcal/mole) than the unreactive quinolinium salt. The unreactivity of isoquinolinium salt can be understood in relation to its high fluorescence quantum yield and its low triplet energy $(E_T = 61 kcal/mole).$.