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논문 기본 정보

자료유형
학위논문
저자정보

민대위 (포항공과대학교, 포항공과대학교 일반대학원)

지도교수
최원용
발행연도
2020
저작권
포항공과대학교 논문은 저작권에 의해 보호받습니다.

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Ice chemistry is relatively new research area and it has attracted a lot of scientific interests due to its unique phenomenon. Not like common sense, chemical reactions could be vigorously occurred in frozen solution because of the existent of a liquid-like layer within the ice structure. This grain boundary in ice was observed from real nature ice samples which shows concentration of inorganic salts in this narrow region. It has been reported that ice in polar region significantly affect surface atmospheric environment of the areas. In polar region, most of surface is covered with ice. The photochemical reaction of nitrate (NO3?) in the ice produce hydroxyl radicals (?OH) which results in the formation of nitrogen oxides, aldehyde, and halogen gases from the polar region surface ice. It could explain the high concentration of active halogen and exceptional chemical composition of troposphere in polar region. Chemical reactions in ice could lead to unexpected consequences and effect on the ecosystem.
Nature ice with liquid-like grain boundary was reproduced in laboratory scale and geochemical reactions in the frozen solution was studied. It has been confirmed that frozen media shows unique chemical reactions which were not found in aqueous condition. In frozen solution nitrite (NO2?) could oxidize phenolic compounds, which results in the formation of phenolic radicals which induce the polymerization of monomers and production of high molecule organic compounds. Decrease of pH in ice grain boundary imposed the formation of nitrosonium (NO+) from nitrite which is strong active oxidant. Specific chemical reactions were dramatically accelerated in frozen solution. Bromate (BrO3?) reduction into bromide was remarkably accelerated in ice while the reduction was negligible in aqueous solution. Hydrogen peroxide (H2O2) generation from cupric ion (Cu2+) and hydroquinone was enhanced in frozen solution than aqueous solution. It was due to the freeze concentration effect during freezing the sample solution. When the solution is freezing solutes are expelled from ice crystal and aggregate in solution, which eventually leads to an increase of concentration in ice grain boundary. However, it was found out that the distribution in frozen solution is different depending on the type of solute. For Cr(III) oxidation, several oxidants showed prohibition of the oxidation under frozen condition. When the oxidant was localized in grain boundary, the chemical reaction was accelerated in frozen condition. In several cases, the oxidants were not concentrated in the liquid-like layer and spread among bulk ice crystal, which results in inhibition of chemical reaction. It identifies that physical behavior of chemical compounds in frozen solution determine the chemical reaction rate in ice.

목차

Contents
1. Research Background
1.1. Ice chemistry 1
1.2. Impacts of ice on ecosystem 9
1.3. References 11
2. Accelerated reduction of bromate in frozen solution
2.1. Introduction 15
2.2. Experimental Section
2.2.1 Reaction in ice 16
2.2.2 Analyses 17
2.3. Results and Discussion
2.3.1 Bromate reduction in dark condition 18
2.3.2 Photo-reduction of bromate 26
2.4. Conclusion 34
2.5. References 35
3. Enhanced H2O2 generation by transition metal and organic compounds in frozen solution
3.1. Introduction 42
3.2. Experimental Section
3.2.1 Reaction in ice 44
3.2.2 Analyses 44
3.3. Results and Discussion
3.3.1 Hydrogen peroxide formation 45
3.3.2 Effect of dissolved organic matter 50
3.3.3 Effect of halide ion 55
3.4. Conclusion 59
3.5. References 60
4. Abiotic formation of humic-like substances through freezing-accelerated reaction of phenolic compounds and nitrite
4.1. Introduction 68
4.2. Experimental Section
4.2.1 Reaction in ice 70
4.2.2 Humic-like acid extraction 70
4.2.3 Analyses 71
4.3. Results and Discussion
4.3.1 Humification of phenols 75
4.3.2 Mass spectrometric analysis 82
4.3.3 Freeze concentration effect 86
4.3.4 Mechanism 86
4.4. Conclusion 91
4.5. References 92
5. Cr(VI) formation via oxyhalide aion-induced oxidative dissolution of chromium oxide/hydroxide in aqueous and frozen solution
5.1. Introduction 97
5.2. Experimental Section
5.2.1 Reaction in ice 99
5.2.2 Cr(OH)3 synthesis 99
5.2.3 Ice grain boundary separation 100
5.2.4 Analyses 101
5.3. Results and Discussion
5.3.1 Cr2O3 oxidation 102
5.3.2 Cr(OH)3 and Cr3+ oxidation 113
5.3.3 Effect of dissolved organic matter 115
5.4. Conclusion 117
5.5. References 118
6. Overall Conclusions 128
Conclusion in Korean 131
Acknowledgements 134
Curriculum Vitae 136

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