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문일식,Subramanian Balaji,Sang Joon Chung,Manickam Matheswaran 한국화학공학회 2007 Korean Journal of Chemical Engineering Vol.24 No.6
mediated electrochemical oxidation (MEO) process with Ce(IV) and nitric acid as the oxidizing me-dium was employed for the destruction of various model organic pollutants in batch and continuous organic feedingmodes. A near complete destruction was observed for all the model organic pollutants studied. The effects of organicconcentration, temperature, concentration of Ce(IV), concentration of nitric acid and feeding time on the organic de-struction efficiency were investigated. Under the experimental conditions of 80oC and 0.95 M Ce(IV) in 3 M nitricacid, nearly 90% destruction was achieved based on CO2 production and 95% based on TOC and COD nearly for allthe organic compounds studied in batch organic addition. In the case of continuous organic addition with in situ electro-regeneration of Ce(IV) by the electrochemical cell a good destruction efficiency was obtained. For long term organicfeeding (120 min) the destruction efficiency was found to be 85% based on CO2 evolution and 98-99% based on TOCand COD analyses. A model was proposed for calculating the CO2 formation constant during the continuous processof organic addition. The model predicted a steady state CO2 evolution pattern for the destruction process during con-onfirmed the predicted trends for the destruction process.The changes in enthalpy, entropy, activation energy and free energy for EDTA degradation were found to be 26.7 kJ/mol, 230 J/(molK), 29.7 kJ/mol, and 118 kJ/mol respectively.
High-energy ion induced physical and surface modifications in antimony sulphide thin films
S. Subramanian,M. Balaji,P. Chithra Lekha,K. Asokan,D. Kanjilal,Indra Sulania,Jai Prakash,D. Pathinettam Padiyan 한국물리학회 2010 Current Applied Physics Vol.10 No.4
Sb2S3 thin films prepared by electrodeposition on indium tin oxide coated glass substrate were irradiated with 150 MeV Ni11+ ions for various fluence in the range of 1011–1013 ions/㎠. The modifications in the structure, surface morphology and optical properties have been studied as a function of ion fluence. X-ray diffraction (XRD) analysis indicates a shift in the (2 4 0) peak position towards lower diffraction angle and a decrease in grain size with increase in ion fluence. Presence of microcracks due to irradiation induced grain splitting effect has been observed from the SEM micrograph at higher ion fluence. The optical absorbance spectrum revealed a shift in the fundamental absorption edge and the band gap energy increased from a value of 1.63 eV for as-deposited films to 1.80 eV for the films irradiated with 1013 ions/㎠.
Manickam Matheswaran,Subramanian Balaji,Sang Joon Chung,문일식 대한화학회 2007 Bulletin of the Korean Chemical Society Vol.28 No.8
The electrochemical oxidation of cerium(III) was carried out using divided and undivided electrochemical cells in nitric acid medium. It was found that divided cell with Nafion 324 as the separator gave good conversion yield with high current efficiency compared to the undivided cell. The efficiency of the divided electrochemical cell was further optimized in terms of cell voltage, temperature, flow rate of solution recirculation, concentrations of Ce(III) and nitric acid. The better conditions for 1 M Ce(III) in 3 M nitric acid were found to be 2.5 V, 363 K and 100 mL/min recirculation flow rate based on the current efficiency under the experimental conditions investigated. The Ce(IV) oxidant produced was used as a mediator for the mineralization of phenol. The mineralization efficiency of the cerium mediated electrochemical oxidation was found rapid and higher compared to the direct electrochemical oxidation based on CO2 evolution under the same conditions.
Matheswaran, Manickam,Balaji, Subramanian,Chung, Sang-Joon,Moon, Il-Shik Korean Chemical Society 2007 Bulletin of the Korean Chemical Society Vol.28 No.8
The electrochemical oxidation of cerium(III) was carried out using divided and undivided electrochemical cells in nitric acid medium. It was found that divided cell with Nafion 324 as the separator gave good conversion yield with high current efficiency compared to the undivided cell. The efficiency of the divided electrochemical cell was further optimized in terms of cell voltage, temperature, flow rate of solution recirculation, concentrations of Ce(III) and nitric acid. The better conditions for 1 M Ce(III) in 3 M nitric acid were found to be 2.5 V, 363 K and 100 mL/min recirculation flow rate based on the current efficiency under the experimental conditions investigated. The Ce(IV) oxidant produced was used as a mediator for the mineralization of phenol. The mineralization efficiency of the cerium mediated electrochemical oxidation was found rapid and higher compared to the direct electrochemical oxidation based on CO2 evolution under the same conditions.
( Kannan Karunakaran ),( Subramanian Balaji ),문일식 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.0
Cyclic voltammetric investigations were carried out with Co(II) dissolved in [bmim]PF6. The CV profiles have indicated that Co(II) undergoes facile oxidation and reduction in both the anodic and cathodic potential regions. As a model pollutant allyl chloride was taken to study the effect of Co(II) catalyzed reduction in the cathodic sweep. It was found that allyl chloride was found to undergo reduction catalytically in the presence of Co(II) ion. The diffusion coefficient of Co(II) in [bmim]PF6 found to range between 0.84 x 10-7 to 11.2 x 10-7 cm2/s in the temperature range 25 - 80°C. The extent of allyl chloride reduction was found by potentiostatic electrolysis and the product formed was analyzed by Fourier Transform Infrared Spectroscopy (FTIR). The electrochemical parameters for the reduction of allyl chloride are calculated and discussed.
Electrolytic production of peroxydiphosphoric acid in an undivided electrolytic batch cell
( Kannan Karunakaran ),( Subramanian Balaji ),김정훈,고윤선,문일식 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.0
The production of oxidants are generally required for various industrial operations for many applications for the removal of trace quantity of organics, metal ion impurities, etc. Peroxydiphosphoric acid is one such strong oxidizing agents and could be produced on demand using an electrolytic cell. Here, we have shown that boron doped diamond (BDD) as the anode and Titanium and Lead as cathodes could be used to generate peroxydiphosphoric acid (H4O8P2) in high yields. The process parameters which influence this electrolytic generation are concentration of the phosphoric acid, temperature and the electrode ratio between anode and cathode. The concentration of the generated peroxy diphosphoric oxidant was found by titrimetry. It was observed that the nature of the cathode also influences the percentage yield of peroxydisulfuric acid to some extent.
( Kannan Karunakaran ),( Subramanian Balaji ),김정훈,이보열,문일식 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.0
Zeolites are complex alumino silicate molecules with specific porosity and pore size distribution. These unique properties make them to be used as molecular sieves in many industrial applications particularly in petrochemical industries. When precursor molecules for the synthesis of zeolites are coated over alumina tubes and subjected to controlled thermal heating, zeolites are formed by in situ growth over the alumina tubes. These tubular materials with coated zeolite materials act as tubular membranes and finds use in electrochemical tubular reactors as the separator. In the present investigation we have employed zeolite coated ceramic membranes for the metal ion oxidation in sulfuric acid medium. Here, we present the results on Cobalt(II) oxidation in sulfuric acid medium carried out under the various process parameters such ascurrent density of the electrodes, metal ion concentration and concentration of the acid electrolyte.
( Kannan Karunakaran ),( Subramanian Balaji ),문일식 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.0
The room temperature ionic liquids (RTILs) find use in many electrochemical applications such as electro deposition, development of gas sensors, organic synthesis, catalysis, solar cells and batteries, synthesis of novel nanostructured materials etc., due to their unique physicochemical properties. In the present report, we present the results of benzene oxidation catalyzed by Co(II) dissolved in N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([bmpyr]+[TFSI]-). In this reaction Co(II) acts as the mediator species and first get oxidized to Co(III). This oxidized species when comes in contact with organic compound oxidizes the organic and getting reduced to Co(I). We have carried out the cyclic voltammetric investigations of Co(II) oxidation and mediated oxidation of benzene. The galvanostatic electrolysis carried out confirmed the catalyzing nature of Co(II) and the oxidation of benzene to benzoquinone.