The effect of hydrogen peroxide on the electrochemical behavior of iron was investigated in perchlorate solutions. Iron showed four distinct behaviors in the perchlorate solutions of pH 3.0. First, the active dissolution regions of Fe with two current waves were observed in the potential range of −0.7 to 0 V (vs. SCE). Second, the stable passivation was found in the potential range between 0 and 0.3 V (vs. SCE). Third, unstable passivation region was observed in the potential range of 0.3 to 1.2 V (vs. SCE). Finally, pitting corrosion was observed at a potential above 1.2 V (vs. SCE). The pH increase stabilized the passivation process of iron, whereas the increase in temperature had a negative influence by enhancing the passivation and pitting behaviors of iron. The presence of hydrogen peroxide at the concentrations below 1.45 mM had an adverse effect on the formation of the passive layer. However, at concentrations above 1.45 mM, hydrogen peroxide affected a beneficial influence on the formation of stable iron oxide layer in the active dissolution region. In addition, regardless of the hydrogen peroxide concentration, the presence of hydrogen peroxide mitigated the pitting corrosion of iron.
In order to prove that perchlorate-laden resins could be bio-regenerated through direct contact with anaerobic microorganisms, two bio-regeneration systems, internal and external, were tested. Anaerobic digestion was demonstrated to be very efficient in degrading perchlorate that had been adsorbed onto A520E resin. The internal bio-regeneration test showed that the fully exhausted resins recovered about 80% of the perchlorate-exchange capacity after 4 weeks of bio-treatment in the anaerobic digester. The bio-regeneration efficiency of the external system increased with the amount of flow passed through the column. Comparison of two perchlorate breakthrough curves obtained from column test, one with virgin resin and the other with bio-regenerated resin, proved that the bio-regenerated resin could be used repeatedly to treat perchlorate in spent or waste brine. The A520E resin was very stable in the anaerobic digester and its perchlorate-exchange capacity was barely changed during 26 weeks of incubation. The most significant contribution of this research is to develop the concept of direct bio-regeneration of exhausted resins by combining physicochemical ion-exchange and biological reduction technology, especially for the removal of perchlorate.
Titanium oxide films and powders are attached onto carbon cloths via RF reactive sputtering and an epoxy resin mixture, respectively. TiO2/carbon composite materials were used to investigate the photoelectrochemical degradation of perchlorate ions in water. The energy band gaps of the RF-sputtered TiO2 thin films ranged from 3.35-3.44 eV. A photocurrent of the powdered TiO2 as illuminated by ultra-violet light for 30 min. was 2.79 mA/cm2. Perchlorate ions in water were shown to be degradable by a UV-illuminated TiO2 powder/carbon/Nafion/carbon composite.
운반체(감응물질)로 제 4급 인산염을 사용하여 PVC를 지지체로 하여 과염소산이온의 농도 10-6 M까지 선형적인 이온선택성 전극을 제작하였다. 운반체의 화학적구조와 함량 가소제의 종류 및 막 두께에 따른 전극의 기울기 선형응답범위 및 한계측정농도 등 전극전위특성을 고려하여 최적의 과염소산 이온선택성 PVC막 전극을 제조한 다음 측정 가능한 pH 범위 선택계수 및 전극의 교류임피던스 특성을 비교 검토하였다 운반체로 tetraoctyl-phosphonium perchlorate(TOPP) tetraphenylphosphonium perchlorate(TPPP) 및 tetrabutylphosponium perchlorate (TBPP) 등의 제 4급 인산염의 과염소산 이온 치환체를 사용하였다 알킬기의 탄소고리 수가 증가할수록 전극특성은 TBPP, 선형응답범위 10-1×10-6 M 및 한계측정농도는 9.66×10-7 M 이었으며 시판되고 있는 Orion 전극특성보다 좋은 결과를 나타내었다 전극전위는 pH3~11범위에서 ph의 영향을 받지 않았으며 CIO4 에 대한 방해이온의 선택계수 서열은 SO24 < F < Br < I 이었다 임피던스 측정결과 TOPP의 경우 등가회로는 용액저항 이중층용량과 벌크저항의 병렬 및 Warburg 임피던스의 직렬이었다 이 경우 용액저항은 거의 나타나지 않았고 확산에 의한 Warburg 임피던스는 크게 나타났으며 Warburg 계수는 1.32×1074 Ω cdot cm2/s1/2이었다.
2-phenyl-N-methyl-1,3-thiazolium perchlorate(PTP)derivatives were synthesized via addition and substitution reactions. PTP was hydrolyzed under aqueous hydrochloride. The structures of the compounds were conformed by N.M.R.,I.R., and elemental analysis.
감응물질로 제4급 암모늄염을 사용하여 PVC를 지지체로 과염소산이온의 농도 10-6M까지 측정가능한 이온 선택성 전극을 제작하였다. 감응물질의 화학적 구조와 함량, 가소제의 종류 및 막 두께에 따른 선형응답 범위와 Nernst의 기울기 등 전극특성을 검토하여, 최적 막조건을 구한 다음 측정가능 pH범위와 여러 방해이온에 대한 선택계수를 비교 검토하였다. 과염소산 이온선택성 전극에서 감응물질의 화학적 구조 즉, 알킬기의 탄소고리수가 증가할수록 선형응답 범위 등 전극 특성은 Aliquat 336P, TOAP, TDAP 및 TDDAP의 순서로 좋아졌다. 가소제는 DBP가 가장 좋았고, 감응물질의 양은 최적 함량 이상에서 적을수록 좋았다. 최적 막 조성은 TDDAP 9.09, PVC 30.3 및 DBP 60.61wt%이었고, 막두께 0.45mm이었다. 이 조건에서 선형응답 범위 10-1~1.2 × 10-6M, 검출한계 5.1×10-7M 및 Nernst기울기 57mV/pClO4이었다. 막전위는 pH 4~11 범위에서 pH의 영향을 받지 않았으며, 선택계수 서열은 다음과 같았다. SCN->I->NO3->Br->ClO3->F->Cl->SO42-