• Bulletin of the Korean Chemical Society
• /
• v.32 no.2
• /
• pp.472-476
• /
• 2011

Sodium chlorate/hydrochloric acid mixtures were used to chlorinate activated arenes and the $\alpha$-position of ketones. This chlorination method was used to produce selectively mono-, di-, and trichlorinated compounds by controlling the molarity of sodium chlorate. This reagent proved to be much more efficient and easier to handle than chlorine gas.

• Journal of Korean Society of Environmental Engineers
• /
• v.31 no.8
• /
• pp.627-634
• /
• 2009

This study was done to find out the formation mechanism of chlorate by electrochemical process using chloride ion ($Cl^-$) as an electrolyte. Firstly, the effective factors such as pH and initial chloride concentration were figured out to see the formation property of chlorate during electrolysis. And the relation of free chlorine, and mixed oxidants such as OH radical and ozone with chlorate were estimated to concretize the formation mechanism. As a result, it was found that the major reaction of chlorate formation would be electrochemical reaction with free chlorine, and also the direct oxidation of chloride ion and the reaction by OH radical were participated in the formation of chlorate. Moreover, it was observed that formed chlorate was oxidized to perchlorate. Lastly, the optimum condition was recommended by comparing free chlorine with chlorate concentration during the electrochemical process with the different electrode separation.

• Proceedings of the Korea Technical Association of the Pulp and Paper Industry Conference
• /
• 2000.11a
• /
• pp.15-21
• /
• 2000

In chlorine dioxide delignification and bleaching the formation of chlorate is undesirable because it does not react with lignin and is harmful to the environment. Chlorate is mainly formed from the in-situ generated hypochlorus acid which is also the main reason for AOX formation. In previous literature scavengers of hypochlorous acid such as sulfamic aicd, DMSO, and hydrogen peroxide have been added to bleaching stages to reduce AOX formation but less attention has been paid to chlorate reduction. This paper thus focuses on the reduction of chlorate content caused by the following additives, sulfamic acid, DMSO, hydrogen peroxide, and oxalic acid. The results show that only sulfamic acid and DMSO reduce chlorate formation under our chlorine dioxide prebleaching conditions. Results by UV spectroscopy and pH adjustment show that scavengers react with hypochlorous acid much faster than with chlorine. Hydrogen peroxide and oxalic acid react with HClO/$Cl_2$much slower than DMSO and sulfamic acid do. The reason for the ineffectiveness of hydrogen peroxide and oxalic acid is ascribed to their slow reaction rates with HClO compared to that of chlorate formation. The fact that only 30-35% of the chlorate can be reduced by sulfamic acid and DMSO when charged in same mole ratio to chlorine dioxide, suggested that the reaction rate of DMSO and sulfamic acid with hypochlorous aicd are of the same magnitude as that of chlorate formation.

• Journal of Korea Technical Association of The Pulp and Paper Industry
• /
• v.30 no.3
• /
• pp.1-6
• /
• 1998

Elementally Chlorine Free (ECF) bleaching will be superior than Totally Chlorine free (TCF) bleaching, not only because they have no significant difference in effluent toxicity, but also those pulps bleached by ECF have higher brightness, strength, yield, etc., over those by TCF. With this belief, this paper focused on the chemistry of chlorine dioxide decomposition and ionization, both in water solution and in pulp slurry. Special attention was paid to chlorate ion because there have been controversies as how it is formed and what its behavior to the end pH of pulp bleaching is. As a result, during ionization of chlorine dioxide with water, both chlorate and chlorite were found to increase with increasing pH, but during ionization with pulp, chlorite was found to increase with end pH while chlorate decreased with increasing end pH. In the case of ionization with water, the disproportion equation $2CIO_2 + OH^{-} \lightarrow H_2O + CIO_3^{-} + CIO_2^{-}$ was thought to become the main reaction with the increasing pH, while in the case of ionization with pulp, the reaction $HCIO + CIO_2^{-}\lightarow H^{+} + Cl^{-} + CIO_3^{-}$ was the main reaction contributing to the formation of chlorate. Based on this above opinion, the contrary results of chlorine dioxide ionization from different researchers were discussed and explained.

• Journal of Korea Technical Association of The Pulp and Paper Industry
• /
• v.31 no.4
• /
• pp.49-57
• /
• 1999

In CLO2 delignification and bleaching process, formation of chlorate corresponds to a loss of 20-36% of the original CKO2 charge. Because chlorate is inactive and harmful to environmental, it will be of benefit to find methods that can reduce the formation of chlorate during chlorine dioxide bleaching. Chlorate is mainly formed by the reaction HCIO +ClO2 $\longrightarrow$H+ + Cl_ +ClO3-2 On the other hand, AOX in chlorine dioxide bleacing is formed also due to the in-situ produced hypochlorous acid. THus both AOX and chlorate could be reduced by addition of hypochlorous acid. Some paper son the reduction of AOX by additives appeared , but systematic data on chlorate reduction as well as pulp and effluent properties are not available. THus this paper of focused on the effects on the reduction of chlorate and chlorine dioxide bleachability. The additives, fulfamic a챵, AMSO, hydrogen peroxide, oxalic acid were found to eliminate chlorine selectively in chlorine and chlorine dioxide mixture.However, when they were added to bleaching process, sulfamic acid and DMSO showed significant reduction of chlorate formation but hydrogen peroxide and oxalic aicd did not, and significant amount ofhydrogen peroxide was found resided in the bleaching effluent , In addition, sulfamic acid and DMSO decreased the bleaching end ph values while hydrogen peroxide and oxalic acid did not, which also indicated that hydrogen peroxide and oxalic acid were ineffective. The difference might be ascribed to the competitives of hypochlorous acid with lignin, chlorite (CKO2) and additives. Sulfamic acid and DMSO showed better pulpbrightness development but less alkaline extraction efficiency than hydrogen peroxide , oxalic acid and control, which means that insitu hypochlorous acid contributes to the formation of new chromophore structures that can be easily eliminated by alkaline extraction. DMSO decreased the delignification ability of chlorine dioxide due to the elimination of hypochlorous acid, but sfulfamic acid did to because the chlroinated sulfamic acid had stable bleachability. In addition, sulfamic acid, and SMSO shwed decreased color and COD of bleaching effluents, hydrogen peroxide decreased effluent color but not COD content, and oxalic acid had no statistically significant effects. No significant decreases of pulp viocosity were found except for hydrogen peroxide. Based on our results , we suggest that the effectiveness of hydrogen peroxide on the reduction of AOX in literature might be explained by other mechanisms not due to the elimination of hypochlorous acid , but to the direct decomposition of AOX by hydrogen peroxide.

• Analytical Science and Technology
• /
• v.30 no.2
• /
• pp.57-67
• /
• 2017

This study was conducted to develop an analytical technique for determination of chlorite and chlorate concentrations in fresh-cut food and dried fish products by an ion chromatography/conductivity detection method using a hydroxide mobile phase. Deionized water was added to homogenized samples, which were then extracted by ultrasound extraction and centrifuged at high speed (8,500 rpm). Subsequently, a Sep-Pak tC18 cartridge was used to purify the supernatant. Chlorite and chlorate ions were separated using 20 mM KOH solution as the mobile phase and Dionex IonPac AS27 column as the stationary phase. Ethylenediamine was used as sample preservative and dibromoacetate was added to adjust for the disparity in extraction efficiencies between the food samples. The method detection limit) for chlorite and chlorate were estimated to be 0.2 mg/kg and 0.1 mg/kg, respectively, and the coefficient of determination ($r^2$) that denotes the linearity of their calibration curves were correspondingly measured to be 0.9973 and 0.9987. The recovery rate for each ion was 92.1 % and 96.3 %, with relative standard deviations of 7.47 % and 6.18 %, respectively. Although neither chlorite nor chlorate was detected in the food samples, the analytical technique developed in this study may potentially be used in the analysis of disinfected food products.

• Analytical Science and Technology
• /
• v.28 no.5
• /
• pp.317-322
• /
• 2015

Simultaneous analytical method has developed for the determination of anion biocides in soil by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Chlorite and chlorate in soil were extracted with pure water, and cyanuric acid and sodium dodecylbenzenesulfonate (Na-DBS) were extracted with mobile phase (0.25 mM ammonium formate in 20 mM formic acid : acetonitrile (1:1)). The extract was injected into the LC-MS/MS system after filtration. The method detection limits in this study were 0.04 mg/kg for chlorite, 0.04 mg/kg for chlorate, 0.27 mg/kg for cyanuric acid, and 0.05 mg/kg for Na-DBS, respectively. The method was applied to the analysis of 50 soil samples collected from 40 sites sprayed with biocides and 10 background sites. As a result, anion biocides were not detected in all sites.

• The Plant Pathology Journal
• /
• v.27 no.2
• /
• pp.128-137
• /
• 2011

Fifty two Macrophomina phaseolina isolates were recovered from 24 host plant species through the 14 Iranian provinces. All isolates were confirmed to species using species-specific primers. The colony characteristics of each isolate were recorded, including chlorate phenotype, relative growth rate at $30^{\circ}C$ and $37^{\circ}C$, average size of microsclerotia, and time to microsclerotia formation. The feathery colony phenotype was the most common (63.7%) on the chlorate selective medium and represented the chlorate sensitive phenotype of the Iranian Macrophomina phaseolina population. Meantime, inter simple sequence repeats (ISSR) Markers were used to assess the genetic diversity of the fungus. Unweighted pair-group method using arithmetic means (UPGMA) clustering of data showed that isolates did not clearly differentiate to the specific group according to the host or geographical origins, however, usually the isolates from the same host or the same geographic origin tend to group nearly. Our results did not show a correlation between the genetic diversity based on the ISSR and phenotypic characteristics. Similar to the M. phaseolina populations in the other countries, the Iranian isolates were highly diverse based on the phenotypic and the genotypic characteristics investigated and needs more studies using neutral molecular tools to get a deeper insight into this complex species.

• Proceedings of the Korea Technical Association of the Pulp and Paper Industry Conference
• /
• 1999.04a
• /
• pp.84-88
• /
• 1999

In chlorine dioxide delignigication or bleaching, chlorate is mainly formed by the reaction between chlorite and hypochlorous acid, thus scavengers of chlorine or hypochlorous acid can be used to reduce the formation of chlorate which is unfavorable to environment. In this study, additives such as sulfamic acid, DMSO, hydrogen peroxide, or sodium chlorite was added to chlorine solution or pure $ClO_2$ solution to check their reactivity with $Cl_2$ and $ClO_2$. These additives were also added directly into general $ClO_2$ solution which contained certain amount of chlorine, then the additive-treated $ClO_2$ solution were used in bleaching stages. The aim of this procedure was to remove the original amount of chlorine that was thought to be possibly the main reason for the formation of chlorate and AOX. The additives were found to be able to eliminate chlorine very fast and selectively, but $H_2$ $O_2$ should be used under pH4, otherwise it also reacts with $ClO_2$. After the additives reacted With $Cl_2$, DMSO turned into an inactive product $(CH_3)_2SO_2$, While Sulfamic acid turned into $HClSO_3H$ that still remained active in oxidation, and $NaClO_2$ produced $ClO_2$. The addition of $HNaClO_2$ showed significant improvement in delignification but the deeper delignification led to higher formation of chlorate. When the additive-treated chlorine dioxide solutions were used in bleaching, both sulfamic acid, DMSO, and hydrogen peroxide showed no significant changes of DE brightness and Kappa number. The formation of chlorate was reduced by addition of sulfamic acid, DMSO and hydrogen peroxide.

• Transactions of the Korean Society of Mechanical Engineers B
• /
• v.41 no.3
• /
• pp.183-189
• /
• 2017

Sodium hypochlorite used in water disinfection processes is generally in the production of chlorine to 0.8％. As the dose of chlorine increases, disinfection by-products (Chlorate) also increase simultaneously and exceed water quality standards. In this study, the electrolytic cell of a sodium hypochlorite generator (12％ chlorine) was adjusted to control the production of the disinfection by-products. As a result, it was possible to reduce Chlorate concentrations by more than 95％ by adjusting the pH of the electrolytic cell from 1.53 to 4.2 (normal pH of the electrolytic cell). As a low current is required to obtain these results, a 15％ improvement in the efficiency of the positive electrode is also observed. For the development of High Sodium Hypochlorite Generation can be used in a safe sodium hypochlorite solution, which is expected to contribute to improvement in the safety of the disinfection process.