• Bulletin of the Korean Chemical Society
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• 제15권10호
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• pp.860-864
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• 1994

2nd-order rate constants have been measured spectrophotometrically for the reactions of 4-nitrophenyl benzoate (1), S-4-nitrophenyl thiobenzoate (2) and 4-nitrophenyl thionbenzoate (3) with alkoxides, aryloxides and thioaryloxides in absolute ethanol at 25.0 ${\pm}0.1$${\circ}C$. The substitution of O by polarizable S in the leaving group has little affected the reactivity of 2 toward the charge localized species (eg. $EtO^-$ and $CF_3CH_2O^-$), while the effect of the similar replacement in the carbonyl group has led to a decrease in reactivity by a factor of 10. However, the reactivity of these esters toward charge delocalized aryloxides has been found to be in the order $1<3{\le}2$. The effect of replaced sulfur atom on reactivity becomes more significant for the reaction with polarizable thioaryloxides, i.e. the reactivity increases in the order $1<2{\ll}3$. The difference in reactivity for the present system is attributed to a polarizability effect.

• Bulletin of the Korean Chemical Society
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• 제11권4호
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• pp.276-281
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• 1990

The equivalent conductance of univalent cation (potassium, silver, thallium and ammonium) perchlorates in methanol containing 18-membered crown ethers, 18-crown-6 (18C6) and 1,10-dithia-18-crown-6 (DT18C6) were measured at different temperatures. The equivalent conductances of ammonium perchlorate were increased by increasing content of DT18C6 exceptionally, due to more favorable solvations than complexations. From the equivalent conductance changes, the formation constants for 1:1 compmlexes have been determined, and the values of enthalpy and entropy changes have been calculated. The complexations of 18C6 and DT18C6 with the univalent cations under investigation are all exothermic and the ${\Delta}$S values are all negative and no considerable differences around 50 J/ (k mol). The selectivity order of 18C6 is $K^+ > Tl^+ > Ag^+ > NH_4^+$, while that of DT18C6 is $Ag^+ > Tl^+ > NH_4^+ > K^+$. By sulfur substitutions in 18C6 result in significant decrease in stability, but the stability of $Ag^+$-DT18C6 complex are $10^4$ times larger than those of $K^+$. This increase of stabilities for $Ag^+$-DT18C6 complex are primary due to the result of favorable exothermic heat of reaction between the polarizable soft cation and soft sulfur centers. In NMR experiment, the stepwise additions of cation perchlorates into crown ether solutions induced two major spectral changes. First, the resonance all shift down field and the cation induced shifts were linear up to 1:1 cation/crown ratio, above which no further changes were observed. On the basis of these results, it could be concluded that 1:1 complex is formed. Second, the magnitudes of cation induced shifts were different each other in same ligand. By addition of silver ion to the solution of DT18C6, the largest shift of proton peak near the sulfur atom was observed. These effects are also arisen from the results of covalent bonding between "soft-soft" interactions.

• 공업화학
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• 제23권4호
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• pp.421-427
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• 2012

초저유황 경유의 윤활성능을 향상시킬 목적으로 식물유 기반 알칸올 아마이드 유도체를 합성하여 윤활성능을 평가하였다. 알칸올 아마이드 유도체는 폐식물유(다크오일), 팜유, 코코넛유를 메탄올과의 연속 전이에스테르화 반응을 통하여 합성한 지방산 메틸에스테르와 디에탄올아민(DEA)의 아마이드화 반응을 행하여 합성하였다. 합성한 알칸올 아마이드 유도체는 1 wt% 범위 내에서 초저유황 경유에 잘 용해되었으며, 이 유도체를 120 ppm 포함한 초저유황 경유의 윤활성능을 HFRR법으로 측정하였다. 그 결과, 초저유황 경유의 마모흔의 직경이 581 ${\mu}m$에서 아마이드 첨가 후 305~323 ${\mu}m$으로 현저히 작아져 초저유황 경유의 윤활성능을 향상하는 것으로 확인되었다. 한편, 식물유의 종류에 따른 마모흔의 차이는 크지 않아 알칸올 아마이드 유도체의 알킬기의 구조에 따른 윤활성능의 차이는 크게 나타나지 않았다. 알칸올 아마이드 한 종류를 선정하여 첨가 농도에 따른 윤활성능을 평가한 결과, 농도에 따라 마모흔의 직경이 현저히 작아지는 결과를 얻었는데 이는 윤활성능이 첨가 농도에 따라 향상되는 것을 의미한다.

• 한국수소및신에너지학회논문집
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• 제19권6호
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• pp.490-497
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• 2008

For continuous operation of the sulfur-iodine(SI) thermochemical cycle, which is expected practical method for massive hydrogen production, suggesting operation conditions at steady state is very important. Especially, in the Bunsen reaction section, the Bunsen reaction as well as side reactions is occurring simultaneously. Therefore, we studied on the relation between the variation of compositions in product solution and side reactions. The experiments for Bunsen reaction were carried out in the temperature range, from 268 to 353 K, and in the $I_2/H_2O$ molar ratio of $0.094{\sim}0.297$ under a continuous flow of $SO_2$ gas. As the result, sulfur formed predominantly with increasing temperature and decreasing $I_2/H_2O$ molar ratios. The molar ratios of $H_2O/H_2SO_4$ and $HI/H_2SO_4$ in global system were decreased as the more side reaction occurred. A side reactions did not appear at $I_2/H_2O$ molar ratios, saturated with $I_2$, irrespective of the temperature change. We concluded that it caused by the increasing stability of an $I_{2x}H^+$ complex and a steric hindrance with increasing $I_2/HI$ molar ratios.

• Bulletin of the Korean Chemical Society
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• 제28권9호
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• pp.1523-1530
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• 2007

The first reduction peak of the cyclic voltammogram (CV) for sulfur reduction in dimethyl sulfoxide has been studied using time resolved Fourier transform electrochemical impedance spectroscopic (FTEIS) analysis of small potential step chronoamperometric currents. The FTEIS analysis results reveal that the impedance signals obtained during short potential steps can be resolved into electron transfer reactions of two different time constants in a high frequency region. The FTEIS method provides snap shots of impedance profiles during an earlier phase of the reaction, leading to time resolved EIS measurements. Our results obtained by the FTEIS analysis are consistent with a series of electron transfer and chemical equilibrium steps of a complex reaction, making up an ECE (electrochemical-chemical-electrochemical) mechanism postulated from the results of computer simulation.

• Bulletin of the Korean Chemical Society
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• 제25권1호
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• pp.73-78
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• 2004

A highly sensitive detecting method has been developed for determining part per billion of sulfur in $H_2S$/Ar plasma. The method is based on the excitation of Ar/$H_2S\;or\;Ar/H_2S/O_2$ mixture in hollow cathode glow discharge sustained by radiofrequency (RF) or 60 Hz AC power and the spectroscopic measurement of the intensity of emission lines from electronically excited $S_2^*\;or\;SO_2^*$ species, respectively. The RF or AC power needed for the excitation did not exceed 30 W at a gas pressure maintained at several mbar. The emission intensity from the $SO_2^*$ species showed excellent linear response to the sulfur concentration ranging from 5 ppbv, which correspond to S/N = 5, to 500 ppbv. But the intensity from the $S_2^*$ species showed a linear response to the $H_2S$ only at low flow rate under 20 sccm (mL/min) of the sample gas. Separate experiments using $SO_2$ gas as the source of sulfur demonstrated that the presence of $O_2$ in the argon plasma is essential for obtaining prominent $SO_2^*$ emission lines.

• 대한화학회지
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• 제58권4호
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• pp.423-427
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• 2014

• 공업화학
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• 제10권4호
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• pp.537-542
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• 1999

석유제품 중의 황화합물을 제거하는 방법으로 미생물에 의한 탈황법이 주목받고 있으며, 이를 위해서는 황화합물의 수용액 상에 대한 용해도를 증가시키는 것이 필수적이라 할 수 있다. 본 연구에서는 가용화제로서 폴리옥시에틸렌(polyoxyethylene, POE)계 비이온 계면활성제를 사용하여 디이젤유 중에 포함되어 있는 황화합물의 가용화도를 X-ray spectrometer를 이용하여 측정하였다. 온도 증가에 따라 황화합물의 가용화도가증가함을 알 수 있었으며, 계면활성제 농도에 따른 가용화도 변화에서는 임계마이셀농도(critical micellar concentration, CMC)보다 높은 1 wt % 이상의 농도 조건에서 가용화도가 급격히 증가 하였다. 본 실험에서 사용한 비이온 계면활성제들 중에서는 가장 소수성을 갖는 계면활성제의 가용화력이 가장 우수하였으며, 특히 동일한 조건에서 소수성기에 branched chain을 가진 Tergitol series 계면활성제가 linear chain을 가진 Neodol series 계면활성제에 비하여 우수한 가용화력을 나타내었다.

• 청정기술
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• 제28권2호
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• pp.97-102
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• 2022

Lithium sulfur (Li-S) batteries have attracted considerable attention as a promising candidate for next-generation power sources due to their high theoretical energy density, low cost, and eco-friendliness. However, the poor electrical conductivity of sulfur and its insoluble discharging products (Li₂S₂/Li₂S), large volume changes, severe self-discharge, and dissolution of lithium polysulfide intermediates result in rapid capacity fading, low Coulombic efficiency, and safety risks, hindering Li-S battery commercial development. In this study, a three-dimensionally (3D) connected hierarchical porous carbon framework (HPCF) derived from waste sunflower seed shells was synthesized as a sulfur host for Li-S batteries via a chemical activation method. The natural 3D connected structure of the HPCF, originating from the raw material, can effectively enhance the conductivity and accessibility of the electrolyte, accelerating the Li⁺/electron transfer. Additionally, the generated micropores of the HPCF, originated from the chemical activation process, can prevent polysulfide dissolution due to the limited space, thereby improving the electrochemical performance and cycling stability. The HPCF/S cell shows a superior capacity retention of 540 mA h g^-1 after 70 cycles at 0.1 C, and an excellent cycling stability at 2 C for 700 cycles. This study provides a potential biomass-derived material for low-cost long-life Li-S batteries.

• 대한화학회지
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• 제35권2호
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• pp.179-183
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• 1991