• 대한화학회지
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• 제14권3호
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• pp.237-242
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• 1970

Effect of Added 1-hexene on the yield of hydrogen produced from Co-60 gamma radiolysis of methanol was investigated at room temperature. The results indicated that the yield of hydrogen decreased rapidly with increasing 1-hexene concentrations. Effect of added methyl borate on the radiolysis of methanol was also studied in the presence of oxygen. The results revealved that methyl borate acted as a less effective scavenger than oxygen towards the precursors of the radiolysis products. Experimental data previously obtained on the systems with oxygen added were treated more quantitatively to re-examine mechanism of the radiolysis of methanol in detail.

• Journal of Photoscience
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• 제8권2호
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• pp.67-69
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• 2001

Radical cations of DPBEY and PPCB were generated by ${\gamma}$-radiolysis and pulse radiolysis in halogenated solvents. The radical cation PPCB+ shows 505 (shoulder) and 520 nm absorption peaks with 700 ns lifetime in agreement with the laser flash photolysis work and strongly support the exciplex mechanism proposed for the photoreaction of PPCB and dimethylfumarate.

• 대한화학회지
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• 제6권1호
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• pp.73-77
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• 1962

Yields of hydrogen, methane, carbon monoxide, formaldehyde and ethylene glycol by gamma-radiolysis of methanol have been determined at room temperature and compared with values reported in the literature. The G-values obtained by the present studies are as follows: $G(H_2)=4.98,\;G(CH_4)=0.28,\;G(CO)=0.09,\;G(HCHO)=2.14\;and\;G(C_2H_6O_2)=3.07.$ The effects of water, methyl borate and alkali halides added to methanol prior to radiolysis have also been investigated. It is observed that alkali iodides and bromides affect the G-values, particularly, of hydrogen, formaldehyde and/or ethylene glycol, whereas alkali chlorides and fluorides have less pronounced effects.

• Nuclear Engineering and Technology
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• 제54권12호
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• pp.4660-4670
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• 2022

Hydroxyurea (HU) is a novel salt-free reductant used potentially for the separation of U/Pu in the advanced PUREX process. In this work, the radiation stability of HU were systematically investigated in solution by examining the effects of the type of rays (α, β, and γ irradiations), the absorbed dose (10-50 kGy), and the HNO₃ concentration (0-3 mol L^-1). The influence degree on HU radiolysis rates followed the order of the absorbed dose > the ray type > the HNO₃ concentration, but the latter two had moderate effects on HU radiolysis products where NH₄⁺ and NO₂^- were found to be the most abundant ones, suggesting that the differences of α, β, and γ rays should be considered in the study of irradiation effects. The radiolysis mechanism was explored using density functional theory (DFT) calculations, and it proposed the dominant radiolysis paths of HU, indicating that the radiolysis of HU was mainly a free radical reaction among ·H, e_aq^-, H₂O, intermediates, and the radiolytic free radical fragments of HU. The results reported here provide valuable insights into the mechanistic understanding of HU radiolysis under α, β, and γ irradiations and reliable data support for the application of HU in the reprocessing of spent fuel.

• Bulletin of the Korean Chemical Society
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• 제9권1호
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• pp.55-59
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• 1988

The gaseous carbon dioxide has been irradiated with Co-60 gamma-radiation in the presence and absence of various alcohols, and the radiolysis products analyzed by gas chromatography. Experimental results indicate that no detectable amount of carbon monoxide is formed when pure carbon dioxide is irradiated. By adding small quantities of alcohols to carbon dioxide, however, considerable amount of carbon monoxide, ketones, alcohols and other organic products have been detected. By adding 0.1% of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-l-propanol, 2-butanol, and 2-methyl-2-propanol, G(CO) values obtained are 4.4, 4.5, 5.2, 4.4, 5.2, 5.0, 4.7 and 4.1, respectively. These high yields of carbon monoxide suggest that the oxidation reactions of carbon monoxide may be suppressed by scavenging oxygen atom with the alcohols. The main radiolytic decomposition reactions of the alcohols present in small quantity in carbon dioxide may be supposed to be the reactions with the oxygen atom produced by the radiolysis of carbon dioxide. The decomposition reactions seems to follow pseudo-first order kinetics with respect to the alcohols. The decomposition rate measured with 2-propanol is the fastest and that with 2-methyl-2-propanol the slowest. The mechanisms of the radiolytic decomposition reactions of the alcohols present in carbon dioxide are discussed on the basis of the experimental results of the present study.

• Journal of Radiation Protection and Research
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• 제31권2호
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• pp.105-113
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• 2006

사용후핵연료의 처분을 위해 사용되는 캐니스터 주변 완충재의 공극 내 지하수는 방사분해에 의해 산화제를 발생한다. 캐니스터 주변의 탄소강의 부식을 결정하는 산화제에 의해 야기된 음 전류 밀도를 계산하기 위하여 수학적 모델을 이용하였다. 실린더 좌표계에서 음 전류 밀도를 구할 수 있는 해석해를 유도하였다. 직교 좌표계와 실린더 좌표계에서 구한 음 전류 밀도를 서로 비교하였다. 방사분해 계산을 위한 선원항 및 흡수선량률은 ORIGEN2와 MCNP 컴퓨터 코드를 이용하여 계산하였다. 새로운 모델을 이용하여 부식을 억제할 수 있는 처분용기 반경을 결정하였다. 계산 결과 실린더 좌표계에서의 해를 이용할 경우 기존의 Marsh 모델보다 음 전류 밀도 값을 25 % 감소시켰다.

• 대한화학회지
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• 제9권2호
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• pp.106-109
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• 1965

메탄올의 Co-60 ${\gamma}$放射線分解反應의 기체 생성물을 기체 크로마토그라피로 정량하는 방법으로 이용함으로써 $B(OCH_3)_3,\;I_2$ 및 KI의 共存이 室溫에서 메탄올의 ${\gamma}$放射線分解에 어떤 영향을 미치는가에 관하여 재검토하였다. $B(OCH_3)_3$이 존재하면 $(CH_2OH)_2$의 收得率은 상당히 감소하고 $H_2$ 및 $CH_2O$의 收得率은 조금 작아지는 경향이 있다. $I_2$가 존재하면 $H_2,\;CH_2O$ 및 $(CH_2OH)_2$의 收得率은 현저히 감소하지만 $CH_4$의 收得率은 약간 감소하는 경향이 있다. KI가 共存하면 $H_2$ 및 $(CH_2OH)_2$의 收得率은 감소하지만 $CH_2O$의 收得率은 증가한다. 위의 어떤 경우에도 미량생성물의 收得率은 거의 변화지 않는다. 이 실험결과를 토대로 하여 메탄올의 放射線分解反應메카니즘을 고찰하였다.

• 분석과학
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• 제21권5호
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• pp.403-411
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• 2008

방사성 액체폐기물의 용매추출 공정에서 발생되는 방사선 분해현상을 연구하기 위하여 추출제로 사용되는 dimethyldibutyltetradecylmalonamide (DMDBTDMA)를 합성하고, 합성된 DMDBTDMA를 $^{60}Co$ 감마 방사선으로 조사시킬 때 생성되는 방사선 분해산물을 정량 분석하였다. 방사선 조사된 DMDBTDMA에 대한 FT-IR 스펙트럼과 EI-질량스텍트럼 및 GC/MS-SIM 방법으로 측정한 결과를 바탕으로 n-methylbutylamine, tetradecane, 1-tetradecanol 3종의 방사선 분해산물의 존재를 확인하였다. 3종의 방사선 분해산물 농도는 이들 표준물질과 n-dodecane을 내부표준물질(ISTD)로 사용하여 GC/MS-SIM 방법으로 정량 분석하였다. 방사선 분해산물에 대한 총 이온 크로마토그램에서 나타난 머무름 거동, 분리도와 해상도 측면에서 만족스런 결과를 얻었으며, 총 이온 크로마토그램에서 n-methylbutylamine, n-dodecane, tetradecane 및 1-tetradecanol 각각의 성분에 대한 피크 검출시간은 각각 2.35분, 8.83분, 10.68분 및 12.75분 이었다. 그리고 tetradecane은 방사선 분해산물의 농도가 DMDBTDMA의 방사선 흡수선량과 비례하는 상관관계를 확인하였다.

• Journal of Photoscience
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• 제10권1호
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• pp.121-126
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• 2003

Irradiation of an acetonitrile solution containing dimethylbis(4-vinylphenylmethyl)silane 1a in the presence of 9,10-dicyanoanthracene leads to formation of the intramolecular photocycloadduct, 2-sila-cyclobuta[2.3]cyclophane(2a). In contrast, prolonged irradiation gave insoluble polymeric material. The photocycloreversion of 2a occurs efficiently (quantum yields exceeds unity) by use of redox-type photosensitization in the presence of magnesium perchlorate. The transient absorption spectra generated by pulse radiolysis and gamma-radiolysis show that the radical cation species generated from 1a is different from that arising from 2a.

• 분석과학
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• 제18권4호
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• pp.292-297
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• 2005

붕산수를 중성자 조사하였을 때 발생하는 화학특성 변화를 측정하였다. 붕산 용액의 pH는 조사시간과 붕산농도가 증가할수록 감소하였다. 물의 방사분해물인 과산화수소는 붕산농도에 비례하였고 조사시간에는 반비례하였다. 기체 방사분해물인 수소와 산소기체는 당량비로 생성되었다. $^{10}B(n{\cdot}{\alpha})^7Li$ 핵반응으로 생성된 Li과 조사시간과의 상관관계는 낮은 붕산 농도범위에서는 좋지 않았으나 높은 농도범위에서는 비례성이 다소 좋아지는 현상을 발견하였다.