• 한국환경과학회지
• /
• 제26권7호
• /
• pp.859-868
• /
• 2017

In this study, the reductive dechlorination of triclosan using zero-valent iron (ZVI, $Fe^0$) and modified zero-valent iron (i.e., acid-washed iron (Aw/Fe) and palladium-coated iron (Pd/Fe)) was experimentally investigated, and the reduction characteristics were evaluated by analyzing the reaction kinetics. Triclosan could be reductively decomposed using zero-valent iron. The degradation rates of triclosan were about 50% and 67% when $Fe^0$ and Aw/Fe were used as reductants, respectively, after 8 h of reaction. For the Pd/Fe system, the degradation rate was about 57% after 1 h of reaction. Thus, Pd/Fe exhibited remarkable performance in the reductive degradation of triclosan. Several dechlorinated intermediates were predicted by GC-MS spectrum, and 2-phenoxyphenol was detected as the by-product of the decomposition reaction of triclosan, indicating that reductive dechlorination occurred continuously. As the reaction proceeded, the pH of the solution increased steadily; the pH increase for the Pd/Fe system was smaller than that for the $Fe^0$ and Aw/Fe system. Further, zero-order, first-order, and second-order kinetic models were used to analyze the reaction kinetics. The first-order kinetic model was found to be the best with good correlation for the $Fe^0$ and Aw/Fe system. However, for the Pd/Fe system, the experimental data were evaluated to be well fitted to the second-order kinetic model. The reaction rate constants (k) were in the order of Pd/Fe > Aw/Fe > $Fe^0$, with the rate constant of Pd/Fe being much higher than that of the other two reductants.

• 대한화학회지
• /
• 제49권6호
• /
• pp.554-559
• /
• 2005

• 대한화학회지
• /
• 제21권4호
• /
• pp.227-234
• /
• 1977

황산산성에서 페닐히드라진과 브롬의 반응을 속도론적으로 검토하였다. 겉보기 2차 반응속도상수는 1M 이하의 황산농도에서는 수소이온 농도에 대략 역비례한다. KBr 첨가의 영향을 검토하여 $Br_2\;및\;Br_3^-$가 반응화학종이고, 이들의 속도상수는 $20^{\circ}C$의 0.01M $H_2SO_4$용액에서 각각 $5{\times}10^5M^{-1},sec^{-1}\;및\;0. 7{\times}10^5M^{-1},sec^{-1}$임을 밝혔다. 2,4-디니트로 페닐히드라진의 브롬과의 반응속도상수는 수소이온 농도에 거의 무관계하며 $Br_2\;및\;Br_3^-$에 대하여 각각 $1.2{\times}10^5M^{-1},sec^{-1}\;및\;2.0{\times}10^4M^{-1},sec^{-1}$이다.

• 동력기계공학회지
• /
• 제21권2호
• /
• pp.14-19
• /
• 2017

The corrosion characteristics of Al-Si-Mg alloy were investigated in $O_2$ and $H_2S/H_2$ environments at high temperature. The weight gain and the reaction rate constant of the Al-Si-Mg alloy were measured in the oxygen and hydrogen sulfide environments at 773K. The weight gain of Al-Si-Mg alloy was showed parabolic increase in the oxygen and hydrogen sulfide environments. The reaction rate constants were confirmed to be $1.45{\times}10^{-4}mg^2cm^{-4}sec^{-2}$ in the oxygen environment and $6.19{\times}10^{-4}mg^2cm^{-4}sec^{-2}$ in the hydrogen sulfide environment respectively. As a result of XPS analysis on the specimen surface, $Al_2O_3$ and MgO compounds were detected in oxygen environment and $Al_2(SO_4)_3$ sulfate was detected in the hydrogen sulfide environment. Corrosion rate of Al-Si-Mg alloy was about 4.3 times faster in hydrogen sulfide environment than oxygen environment.

• 대한화학회지
• /
• 제41권8호
• /
• pp.385-391
• /
• 1997

Co$(dimethyl bipyridine)_3(ClO_4)_2$의 확산계수$(D_0)$와 전극반응속도상수$(K_0)$를 순환전압전류법과 대시간전류법으로 구하였다. 확산계수에 대한 용매, 농도, 주사속도 등의 영향과 반응속도상수에 대한 온도변화의 영향을 조사하였다. 25$^{\circ}C$에서 확산계수는 $5.54{\times}10^{-6 }cm^2/sec$이었고, 반응속도상수는 $2.39{\times}10^{-3 }/s$ 이었으며, 용매의 점도가 커질수록 봉우리전류값과 확산계수는 감소하였다. 반응속도상수에 대한 온도의 영향으로부터, ${\Delta}G^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S$ 등의 열역학적 파라미터를 구하였다. 이 화합물은 $O_2$분자의 환원에서 봉우리전류를 크게 증가시키고, 환원전위를 양(+)전위방향으로 이동시키는 열역학적 전극촉매현상을 보였다.

• 대한화학회지
• /
• 제58권1호
• /
• pp.17-24
• /
• 2014

The oxidative decarboxylation of phenylsulfinylacetic acid (PSAA) by Cr(VI) in 20% acetonitrile -80% water (v/v) medium follows overall second order kinetics, first order each with respect to [PSAA] and [Cr(VI)] at constant [$H^+$] and ionic strength. The reaction is acid catalysed, the order with respect to [$H^+$] is unity and the active oxidizing species is found to be $HCrO_3^+$. The reaction mechanism involves the rate determining nucleophilic attack of sulfur atom of PSAA on chromium of $HCrO_3^+$ forming a sulfonium ion intermediate. The intermediate then undergoes ${\alpha}$,${\beta}$-cleavage leading to the liberation of $CO_2$. The product of the reaction is found to be methyl phenyl sulfone. The operation of substituent effect shows that PSAA containing electron-releasing groups in the meta- and para-positions accelerate the reaction rate while electron withdrawing groups retard the rate. An excellent correlation is found to exist between log $k_2$ and Hammett ${\sigma}$ constants with a negative value of reaction constant. The ${\rho}$ value decreases with increase in temperature evidencing the high reactivity and low selectivity in the case of substituted PSAAs.

• 한국응용과학기술학회지
• /
• 제25권4호
• /
• pp.418-428
• /
• 2008

Transesterification of fat of Tra catfish with methanol in the presence of the KOH catalyst yields fatty acid methyl esters (FAME) and glycerol (GL). The effects of the reaction temperature and reaction time on rate constants and kinetic order were investigated. Three regions were observed. In the initial stage, the immiscibility of the Tra fat and methanol limited the reaction rate, hence this region was controlled by the mass transfer. Subsequent to this region, produced FAME like a co-solvent made the reaction mixture homogeneous, therefore the conversion rate increased rapidly so it was controlled by the kinetic parameters of the reaction until the equilibrium was approached in the final slow region. A second-order kinetic mechanism was proposed involving second regions for the forward reaction. The rate determining step for the overall KOH catalyzed-methanolysis of Tra fat was the conversion of triglycerides (TG) to diglycerides (DG). This rate constant was increased from 0.003 to $0.019min^{-1}$ when the reaction temperature was increased from 35 to $60^{\circ}C$. Its calculated activation energy was 14.379 ($kcal.mol^{-1}$).

• 폴리머
• /
• 제29권3호
• /
• pp.304-307
• /
• 2005

산을 촉매로 한 물/초산용액에서의 폴리(비닐 아세테이트) 가수분해반응을 $35^{circ}C$에서, 물과 초산치 비율을 달리한 두 용액 조성에서 연구하였다. 반응시간에 따른 비닐 아세테이트(VAc)와 비닐 알코올(VA) 단량체 몰분율을 NMR로 측정하였고, 반응이 평형에 도달한 후의 화학평형상수($K_{eq}$)를 화학평형상태에서의 VAc와 VA의 몰분율을 이용하여 결정하였다. 화학평형에서의 VAc 몰분율이 0.78(${\pm}0.01$)이었을 때 $K_{ef}$는 0.76(${\pm}0.01$)이었고, VAc 몰분율이 0.57(${\pm}0.02$)일 때 0.69($\{pm}0.01$)이었다. 가수분해반응은 가성 1차 반응을 따랐으며, 반응속도상수는 $3.4{\times}10^{-6}/sec$이었다.

• 한국식품조리과학회지
• /
• 제11권4호
• /
• pp.396-400
• /
• 1995

The antioxidant effects in soybean oil was investigated by browning reaction mixtures formed by sugar and reaction temperatures above 110$^{\circ}C$. 0.1 M solution of xylose, glucose and sucrose were heated at 110, 120, 130, 140 and 150$^{\circ}C$ for 24 hrs respectively. A reaction rate constant(k), activation energy (Ea) and Q$\sub$10/ value were determined by color intensity that was measured absorbance at 490 nm in each temperature. Soybean oil containing the ethanol extracts taken from the browning reaction mixtures that were heated at 110, 130 and 150$^{\circ}C$ was stored in an incubator kept at 45.0${\pm}$1.0$^{\circ}C$ for 24 days. The results are as follows: 1. When 0.1 M solution of xylose, glucose and sucrose were heated at 110$^{\circ}C$ and 120$^{\circ}C$, the intensity of glucose browning mixtures was the highest, but heated at 150$^{\circ}C$, the color intensity increased in order of xylose > glucose > sucrose after 24 hrs. 2. The reaction rate constant (k) was increased rapidly above 140$^{\circ}C$ and appeared maximum at 150$^{\circ}C$, esp. xylose was the highest. The activation onergy (Ea) of xylose was the highest as 93.28 Joule/mole and the Q$\sub$10/ value of xylose was appeared 1.28. Q$\sub$10/ value was also the highest in xylose. 3. The browning reaction mixtures that were heated at 110$^{\circ}C$ appeared little antioxidant effects. But, in heated at 130$^{\circ}C$ and 150$^{\circ}C$, the antioxidant effects appeared in sucrose browning reaction mixtures. Therefore, in browning reaction mixtures that heated above 110$^{\circ}C$, only sucrose browning reaction mixtures appeared antioxidant effects and xylose, glucose appeared little antioxidant effects. On the contrary xylose and glucose increased peroxide values of soybean oil.

• Bulletin of the Korean Chemical Society
• /
• 제11권4호
• /
• pp.343-347
• /
• 1990

A thermal decomposition of the tert-butoxy radical has been studied in the gas phase over the pressure range of 1-200 torr at $413_{\circ}K$ using di-tert-butyl peroxide + trimethylsilane mixtures. The relative rate constants were obtained by studying the competitive reactions between tert-butoxy radical decomposition 4(t-BuO·→ CH_3COCH_3 + CH_3·)$ and hydrogen abstraction reaction from trimethylsilane $(t-BuO·+ HSi(CH_3)_3 → t-BuOH + Si(CH_3)_3)·).$ The conventional RRKM calculations were carried out to compare the observed fall-off behavior of the decomposition rate constant $({\kappa}_d)$ with the theoretical predictions using reasonable values of input parameters. In all cases the calculated half-rate pressure $(P_{1/2})$ were significantly higher than those observed. The failure of RRKM to reproduce the fall-off behavior led us to suggest that not all of vibrational modes contribute to excitation (leading to decomposition) on the same time scale.