• Journal of Environmental Science International
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• v.5 no.5
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• pp.569-577
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• 1996

pure compound chloromethanes; methyl chloride, methylene chloride, chloroform and The carbon tetrachloride were used as a model of chlorocarbon system with Cl/H ratio to investigate thermal stability and hydrodechlorination process of carbon tetrachloride under excess hydrogen atmosphere. The parent thermal stability on basis of temperature required for 99% destruction at 1 second no was evaluated as $875^{\circ}C$ for $CH_3Cl$, $780^{\circ}C$ for $CH_2Cl_2$, $675^{\circ}C$ for $CHCl_3$ and $635^{\circ}C$ for $CCl_4$. Chloroform was thermally less stable than $CCl_4$ at fairly low temperatures $(<570^{\circ}C).$ The lion of $CCl_4$ became more sensitive to increasing temperature, and $CCl_4$ was degraded CHCl3 at above $570^{\circ}C.$ The number and quantity of chlorinated products decreases with increasing temperature for the Product distribution of $CCl_4$ decomposition reaction system. Formation of non-chlorinated hydrocarbons such as $CH_4$, $C_2H_4$ and C_2H_6$ increased as the temperature rise and particularly small amount of methyl chloride was observed above $850^{\circ}C$ in $CC1_4$/$H_2$ reaction system. The less chlorinated products are more stable, with methyl chloride the most stable chlorocarbon in this reaction system.

• Analytical Science and Technology
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• v.19 no.6
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• pp.504-511
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• 2006

Polysilanes with organic substituents such as methyl and phenyl were synthesized by Wurtz dechlorination-condensation reactions using ultrasonic from organochlorosilanes. The yields were compared with the results of thermal dechlorination-condensation reactions. Properties such as thermogravimetric analysis and photoreactivity were investigated for the possibility of applications.

• Journal of Soil and Groundwater Environment
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• v.13 no.1
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• pp.92-100
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• 2008

Experimental studies were conducted to identify the active agents for reductive dechlorination of TCE in cement/Fe(II) systems focusing on cement components such as CaO, $Fe_2O_3$, and $Al_2O_3$. A hematite that was used to simulate an $Fe_2O_3$ component in cement was found to have degradation efficiencies (k = 0.641 $day^{-1}$) equivalent to that of cement/Fe(II) systems in the presence of CaO/Fe(II), only when it contained an aluminum impurity$(Al_2O_3)$. When the effect of $Al_2O_3$ content of hematite/CaO/$Al_2O_3$/Fe(II) system was tested, the mole ratio of $Al_2O_3$ to CaO affected the rate of TCE degradation with an optimum ratio around 1 : 10 that resulted in a rate constant of 0.895 $day^{-1}$. In the SEM images of hematite/CaO/$Al_2O_3$/Fe(II) systems, acicular crystals were also found that were also observed in cement/Fe(II) systems. Thus it was suspected that these crystals were reactive reductants and that they might be goethite or ettringite that are known to have acicular structures. An EDS element map analysis revealed that these crystals were not goethite crystals. A subsequent experiment that tested reactivities of compounds formed during the ettringite synthesis showed that ettringite and minerals associated with ettringite formation are not reactive reductants. These observations conclude that a mineral containing CaO and $Al_2O_3$ with a acicular structure could be a major reactive reductant of cement/Fe(II) systems.

• Analytical Science and Technology
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• v.21 no.3
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• pp.201-211
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• 2008

The treatment efficiency of PCBs containing wastes has been investigated. The samples treated by electron beam and de-chlorination method were analyzed to verify the byproducts before treatment and after treatment. In the treated samples by electron beam irradiation, PCBs were not detected by comparing the peak matching using the Korean official waste test method. On the other hand, PCBs congeners were detected by analyzing individual isotope method using HRGC/HRMS. Most of PCB congeners in waste were decomposed to 3-chlorobiphenyls, lower chlorinated congener produced during the treatment of electron beam. In the chemical dechlorination treatment, it was found that the concentrations of PCBs in treated samples were lower than those of regulation criteria in Waste & POPs management law and the after treatment concentration were satisfied to the regulation criteria. Also, dioxins were not observed after the physio-chemical treatment processes of PCBs containing wastes.

• Korean Chemical Engineering Research
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• v.49 no.5
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• pp.510-515
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• 2011

The pyrolytic reaction of 1,1-dichloroethylene($CH_2CCl_2$) has been conducted to investigate thermal decomposition of chlorocarbon and product formation pathways under hydrogen reaction environment. The reactions were studied in a isothermal tubular flow reactor at 1 atm total pressure in the temperature range $650{\sim}900^{\circ}C$ with reaction times of 0.3~2.0 sec. A constant feed molar ratio $CH_2CCl_2:H_2$ of 4:96 was maintained through the whole experiments. Complete decay(99%) of the parent reagent, $CH_2CCl_2$ was observed at temperature near $825^{\circ}C$ with 1 sec. reaction time. The important decay of $CH_2CCl_2$ under hydrogen reaction environment resulted from H atom cyclic chain reaction by abstraction and addition displacement. The highest concentration (28%) of $CH_2CHCl$ as the primary product was observed at temperature $700^{\circ}C$, where up to 46% decay of $CH_2CCl_2$ was occurred. The secondary product, $C_2H_4$ as main product was detected at temperature above $775^{\circ}C$. The one less chlorinated ethylene than parent increase with temperature rise subsequently. The HCl and dechlorinated hydrocarbons such as $C_2H_4$, $C_2H_6$, $CH_4$ and $C_2H_2$ were the main products observed at above $825^{\circ}C$. The important decay of $CH_2CCl_2$ resulted from H atom cyclic chain reaction by abstraction and addition displacement. The important pyrolytic reaction pathways to describe the features of reagent decay and intermediate product distributions, based upon thermochemical and kinetic principles, were suggested.

• Applied Biological Chemistry
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• v.17 no.3
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• pp.149-176
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• 1974

Eight substituted diphenyl ether herbicides and some of their photoproducts were studied in terms of solution phase photolysis under simulated environmental conditions by using a Rayonet photochemical reactor. The test compounds absorbed sufficient light energy at the wavelength of 300 nm to undergo various photoreactions. All the photoproducts were confirmed by means of tlc, glc, ir, ms, and/or nmr spectrometry. The results obtained are summarized as follows: Solution phase photolysis of C-6989: An exceedingly large amount of p-nitrophenol formed strongly indicates the readiness of the ether linkage cleavage of this compound as the main reaction in all solvents used. Photoreduction of nitro to amino group(s) and photooxidation of trifluoromethyl to carboxyl group were recognized as minor reactions. Aqueous photolysis of p-nitrophenol: Quinone(0.28%), hydroquinone (0.66%), and p-aminophenol (0.42%) were confirmed as photoproducts, in addition to a relatively small amount of an unknown compound. The mechanisms of formation of these products were proposed to be the nitro-nitrite rearrangement via $n{\rightarrow}{\pi}^*$ excitation and the photoreduction through hydrogen abstractions by radicals, respectively. Solution phase photolysis of Nitrofen: Photochemical reduction leading to the p-amino derivative was the main reaction in n-hexane. In aqueous solution, the photoreduction of nitro to amino group and hydroxylation predominated over the ether linkage cleavage. Nucleophilic displacement of the nitro group by hydroxide ion and replacement of chlorine substituents by hydroxyl group or, to a lesser extent, hydrogen were also observed as minor reactoins. Solution phase photolysis of MO-338: Photoreduction of the nitro to amino group was marked in the n-hexane solution photolysis. In the aqueous solution, photoreduction of the nitro substituent and hydroxylation were the main reactions with replacement of chlorine substituents by the hydroxyl group and hydrogen, and cleavage of the ether linkage as minor reactions. Photolyses of MC-4379, MC-3761, MC-5127, MC-6063, and MC-7181 in n-hexane and cyclohexane: Photoreduction of the nitro group leading to the corresponding amino derivative and replacement of one of the halogen substituents by hydrogen from the solvent used were the key reactions in each compound. Aqueous photolysis of MC-4379: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, hydroxylation, and replacement of the nitro by hydroxy group were prominent with photoreduction and dechlorination as minor reactions. Aqueous photolysis of MC-3761: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, and photoreduction followed by hydroxylation were the main reactions. Aqueous photolysis of MC-5127: Replacement of carboxyethyl by hydrogen was predominant with ether linkage cleavage, photoreduction, and dechlorination as minor reactions. It was obvious that the decarboxyethylation proceeded more readily than decarboxymethylation occurring in the other compounds. Aqueous photolysis of MC-6063: Cleavage of the ether linkage and photodechlorination were the main reactions. Aqueous photolysis of MC-7181: Replacement of the carboxymethyl group by hydrogen and monodechlorination were the remarkable reactions. Cleavage of the ether linkage and hydroxylation were thought to be the minor reactions. Aqueous photolysis of 3-carboxymethyl-4-nitrophenol: The photo-induced Fries rearrangement common to aromatic esters did not appear to occur in the carboxymethyl group of this type of compound. Conversion of nitro to nitroso group was the main reaction.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2000.11a
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• pp.119-123
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• 2000

In-situ treatment technologies have been proposed to transform or remove pollutants from contaminated groundwater. Zero-valent iron(Fe$^{0}$ ), metallic iron, is being evaluated as a permeable reactive material to retard the transport of wide array of highly mobile contaminants in groundwater. In this research, tetrachloroethylene(PCE) dechlorination by powdered zero-valent iron in buffered aqueous solution was studied with and without the presence of surfactants. The rate of dechlorination of PCE by zero-valent iron with surfactant was much higher than without surfactant. The presence of surfactant increased the apparent rate of dechlorination because the surfactants influenced the dissolution of PCE into the aqueous phase.

• Clean Technology
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• v.16 no.3
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• pp.198-205
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• 2010

Two sets of thermal reaction experiment for chlorinated hydrocarbons were performed using an isothermal tubular-flow reactor in order to investigate thermal decomposition, including product distribution of chlorinated hydrocarbons. The effects of $H_2$ or Ar as the reaction atmosphere on the thermal decomposition and product distribution for dichloromethane($CH_2Cl_2$) was examined. The experimental results showed that higher conversion of $CH_2Cl_2$ was obtained under $H_2$ atmosphere than under Ar atmosphere. This phenomenon indicates that reactive-gas $H_2$ reaction atmosphere was found to accelerate $CH_2Cl_2$ decomposition. The $H_2$ plays a key role in acceleration of $CH_2Cl_2$ decomposition and formation of dechlorinated light hydrocarbons, while reducing PAH and soot formation through hydrodechlorination process. It was also observed that $CH_3Cl,\;CH_4,\;C_2H_6,\;C_2H_4$ and HCl in $CH_2Cl_2/H_2$ reaction system were the major products with some minor products including chloroethylenes. The $CH_2Cl_2$/Ar reaction system gives poor carbon material balance above reaction temperature of $750^{\circ}C$. Chloroethylenes and soot were found to be the major products and small amounts of $CH_3Cl$ and $C_2H_2$ were formed above $750^{\circ}C$ in $CH_2Cl_2$/Ar. The thermal decomposition reactions of chloroform($CHCl_3$) with argon reaction atmosphere in the absence or the presence of $CH_4$ were carried out using the same tubular flow reactor. The slower $CH_3Cl$ decay occurred when $CH_4$ was added to $CH_3Cl$/Ar reaction system. This is because :$CCl_2$ diradicals that had been produced from $CHCl_3$ unimolecular dissociation reacted with $CH_4$. It appears that the added $CH_4$ worked as the :$CCl_2$ scavenger in the $CHCl_3$ decomposition process. The product distributions for $CHCl_3$ pyrolysis under argon bath gas were distinctly different for the two cases: one with $CH_4$ and the other without $CH_4$. The important pyrolytic reaction pathways to describe the important features of reagent decay and intermediate product distributions, based upon thermochemistry and kinetic principles, were proposed in this study.

• Journal of Soil and Groundwater Environment
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• v.9 no.2
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• pp.11-19
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• 2004

Chlorinated and nitroaromatic compounds are non-degradable substances that are extremely toxic and are known to be carcinogens and mutation causing agents. Moreover, the half-lives of substances such as carbon tetrachloride, hexachloroethane and nitroaromatic compounds are several decades. In this study, the optimal conditions to detoxify chlorinated compounds by the reductive degradation were investigated. The following results were obtained in the reductive degradation of CCl$_4$, C$_2$Cl$\_$6/, C$_2$HCl$\_$5/, C$_2$Cl$_4$, and C$_2$HCl$\_$5/ by using Fe, FeS and FeS$_2$ as mediators. CCl$_4$ was reduced to CH$_2$Cl$_3$ and CH$_2$Cl$_2$in anaerobic conditions when FeS was used as a mediator. While the reduction of CCl$_4$ to CHCl$_3$ was rapidly proceeded, the reduction of CHCl$_3$ to CH$_2$Cl$_2$ was occurred slowly. Further reduction to CH$_3$Cl was not observed. Unlike CCl$_4$, C$_2$Cl$\_$6/ was degraded to C$_2$HCl$\_$5/, C$_2$Cl$_4$. C$_2$HCl$_3$ and cis-1,2-C$_2$H$_2$Cl$_2$ by complicated pathways such as hydrogenolysis, dehalo-elimination and dehydrohalogenation. A small amount of C$_2$HCl$\_$5/ was detected only in the early stages of the reduction. However, majority of the C$_2$Cl$\_$6/ was reduced to C$_2$Cl$_4$. cis-1,2-C$_2$H$_2$C1$_2$ was the only product among other possible isomers.

• Economic and Environmental Geology
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• v.35 no.3
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• pp.229-239
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• 2002

The objective of this study was to design an optimal electro-remediation system for TCE contaminated water using zero talent iron (ZVI) and direct current (DC). A series of column experiments were conducted to evaluate the effects of electrode arrangement and the location of permeable iron barrier in the column on the TCE removal efficiency and iron corrosion process. In twelve different combinations of ZVI and/or DC application in the test columns, the rate of reductive degradation of TCE was improved with simultaneous application of both ZVI and DC compared to that used ZVI only. The moot effective arrangement of electrode and ZVI for TCE removal from water was a column set with ZVI and cathode installed at the down gradient, respectively.