• Bulletin of the Korean Chemical Society
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• 제17권9호
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• pp.802-807
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• 1996

Second-order rate constants have been measured spectrophotometrically for the reactions of aryl benzoates (X-C6H4CO2C6H4-Y) with EtO-, Z-C6H4O- and Z-C6H4C(Me)=NO- in absolute ethanol at 25.0 ℃. All the reactions have been performed in the presence of excess 18-crown-6 ether in order to eliminate the catalytic effect shown by alkali metal ion. A good Hammett correlation has been obtained with a large ρ- value (-1.96) when σ- (Z) constant was used for the reaction of p-nitrophenyl benzoate (PNPB) with Z-C6H4O-. Surprisingly, the one for the reaction of PNPB with Z-C6H4C(Me)=NO- gives a small but definitely positive ρ- value (＋0.09). However, for reactions of C6H5CO2C6H4-Y with EtO-, correlation of log k with σ- (Y) constant gives very poor Hammett correlation. A significantly improved linearity has been obtained when σ0 (Y) constant was used, indicating that the leaving group departure is little advanced at the TS of the RDS. For reactions of X-C6H4CO2C6H4-4-NO2 with EtO-, C6H5O- and C6H5C(Me)=NO-, correlations of log k with σ (X) constants for all the three nucleophile systems give good linearity with large positive ρ values, e.g. 2.95, 2.81 and 3.06 for EtO-, C6H5O- and C6H5C(Me)=NO-, respectively. The large ρ values clearly suggest that the present reaction proceeds via a stepwise mechanism in which the formation of the addition intermediate is the RDS.

• 대한환경공학회지
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• 제30권10호
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• pp.1039-1046
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• 2008

수중에 존재할 수 있는 항생제물질 중 cefaclor를 제거하기 위하여 UV/H$_2$O$_2$ 공정을 적용하였다. 기존 회분식반응기의 경우 시료를 채취하면 시료가 감소하여 UV램프와 제거대상물질의 유효접촉면적이 감소하는 것을 보완하기 위해 외부에 혼합조를 설치하여 실험을 실시하였다. UV반응기 내부는 완전혼합을 위해 4개의 baffle을 설치하였으며 광자의 방출을 방지하기 위해 반응조 외부를 알루미늄 호일로 감쌌다. OH radical의 생성은 pCBA(p-Chlorobenzoic acid)를 이용하여 간접적으로 측정하였으며, 의사일차반응식(pseudo-frist order reaction)을 이용하여 반응속도상수를 구하였다. 본 연구의 최적 OH radical 생성조건은 pH 3, 과산화수소 주입량은 5 mmol/L 그리고 펌프순환유량은 400 mL/min로 나타났으며, 반응속도상수는 0.1051 min$^{-1}$이었다. 최적의 OH radical 생성조건에서 cefaclor는 40 min안에 완전히 제거되었으며 반응속도상수는 0.093 min$^{-1}$이었다. 초기 cefaclor의 농도가 낮을 수록 빠르게 제거되었으며, OH radical에 의해 분해되어 중간생성물질(intermediates)인 chloride(Cl$^-$), nitrate(NO$_3{^{2-}}$), sulfite(SO$_4{^{2-}}$) 그리고 acetic acid(CH$_3$COO$^-$) 등의 음이온과 phenylglycine을 생성하였다. 반응시간 6 hr 이후 TOC의 77% 감소, phenylglycine의 소멸 그리고 acetic acid가 감소하는 것으로 보아 cefaclor는 UV/H$_2$O$_2$ 공정에 의해 빠르게 분해될 뿐만 아니라 CO$_2$와 H$_2$O의 형태로 무해화(mineralization)되는 것으로 보인다.

• Bulletin of the Korean Chemical Society
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• 제6권5호
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• pp.291-295
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• 1985

The efficiency of photosensitization of methyl linoleate (ML) oxidation by N-acetyl-L-trypophan(NAT) and 3-methyl indole(scatole) was markedly enhanced by increased concentration of ML in ethanol solution. The fluorescence intensities of sensitizers were observed to be quenched by ML, indicating that ML interacts with the indole excited singlet state. The inhibition of photosensitization by azide demonstrated a possible role of singlet oxygen in the photosensitization. The steady state kinetic treatment of azide inhibition of photosensitization was expected to show linear increase of reciprocal yield of ML oxidation product vs. reciprocal ML concentration at constant azide concentration, but the actual slope was nonlinear. This indicates another competing reaction involved in the photosensitization, As a possible competing reaction, electron transfer from ML to the excited sensitizer was proposed, since the measured fluorescence quenching rate constant closely resembled electron transfer rate constant determined from ML concentration dependence of oxidation product formation.

• 대한화학회지
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• 제39권10호
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• pp.769-775
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• 1995

메틸 라디칼과 산소 분자 사이의 반응 속도를 입사 충격파를 이용하여 1390부터 2250k 온도범위 및 1.5에서 5.3mol/$m^3$ 밀도 범위에서 213.9nm 파장에서의 메틸 라디칼의 흡수 스펙트럼을 측정하여 고찰하였다. 메틸 라디칼을 생성하기 위한 원천 분자로는 azomethane이 사용되었다. 실험 결과 $CH_3 + O_2{\rightarrow}CH_2O + OH$ 반응의 속도상수는 $k_2=1.35{\times}10^{12}\;exp( - 5900 K/T)\;cm^3 mol^{-1}s^{-1}$ 같이 표현할 수 있었다.

• 대한화학회지
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• 제54권2호
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• pp.208-214
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• 2010

포스포리파제 D(PLD)는 알코올 존재 하에서 포스파티딜 전달반응이 일어나며 동시에 PLD의 전체 반응속도도 증가하는 것으로 알려져 있다. 이 포스파티딜 전달반응을 자세히 구명하기위해 본 실험에서는 양배추에서 정제한 ${\alpha}$-type PLD를 가지고 여러 종류의 알코올 존재 하에서 포스파티딜 전달반응의 반응속도를 검토하였다. 실험 결과 검토한 1차 알코올들에 의해 PLD의 포스파티딜 전달반응 속도는 기대했던 대로 크게 증가하였다. 부탄올의 경우 2차 반응속도는 $33.33{\pm}1.33M^{-1}sec^{-1}$로 얻어졌으며, 이 전달반응 속도를 물의 농도를 고려한 가수분해 속도($0.078M^{-1}sec^{-1}$)와 비교하면 무려 400배 이상의 격차를 보여주었다. 알코올의 $pK_a$과 포스파티딜 전달반응 속도와의 자유에너지 선형 관계로부터 브뢴스테드 ${\beta}_{nu}$ 값 $0.12{\pm}0.03$을 얻었다. 비교적 적은 ${\beta}_{nu}$ 값으로 미루어보아 끊어지는 포스파티딜-효소 중간체(E-P)의 전이상태는 상당히 해리된 상태일 것으로 추정된다. 이들 결과와 양배추 PLD의 활성부위의 히스티딘 잔기를 참작하여 양배추 PLD의 반응메커니즘을 제안하였다.

• 공업화학
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• 제16권1호
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• pp.153-157
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• 2005

$H_2O$ 용매하에서 4-(dimethylamino)pyridine과 chromium(VI) trioxide의 반응을 통하여 4-(dimethylamino)pyridinium dichromate를 합성하여, IR, EA 및 ICP 등으로 구조를 확인하였다. 여러 가지 용매하에서 4-(dimethylamino)pyridinium dichromate를 이용하여 벤질 알코올의 산화반응을 측정한 결과 유전상수 값이 큰 용매 순서인 시클로헥센 < 클로로포름 < 아세톤 < N,N-디메틸포름아미드 용매에서 높은 산화반응성을 보였다. 산 촉(HCl)를 이용한 N,N-디메틸포름아미드 용매하에서 4-(dimethylamino)pyridinium dichromate는 벤질 알코올과 그의 유도체들($p-CH_3$, H, m-Br, $m-NO_2$)을 효과적으로 산화시켰다. 그리고 전자받개 그룹들은 반응속도가 감소한 반면에 전자주개 치환체들은 반응속도를 증가시켰다. 또한 Hammett 반응상수 $\rho$값은 -0.70(303 K)이였다. 그러므로 본 실험에서 알코올의 산화반응 과정은 먼저 크토메이트 에스테르 형성과정을 거친 후, 속도결정단계에서 양성자 전이가 일어나는 메카니즘임을 알 수 있었다.

• 한국결정성장학회지
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• 제1권1호
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• pp.92-99
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• 1991

$Si(OC_2H_5)_4$ 로부터 $SiO_24$ 미립자를 얻는 반응은 가수분해반응과 종합반응의 두 단계로 이루어지며 중합반응은 $Si(OC_2H_5)_4$의 농도에 대하여 1차 반응이었다. 중합반응의 반응속도상수는 물의 농도와 촉매의 농도가 증가할수록 그리고 반응온도가 높아질수록 커지는 경향을 나타내고 있다. 생성된 실리카의 직경은 $0.06-0.27\mu\textrm{m}$이었으며 직경은 $Si(OC2H5)4$의 초기농도가 작아질수록 온도가 시간에 따라 입자가 성장해가는 속도는 전화율의 함수로 d=a.ln(Xa)+b 의 형태로 나타낼 수 있으며 최종 실리카의 직경은 사수 b값에 접근하였다.

• 한국재료학회지
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• 제26권8호
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• pp.406-411
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• 2016

In order to reuse the photocatalyst and enhance the photolysis efficiency, we have used atmospheric pressure dielectric barrier discharge (APDBD) to clean and activate $TiO_2$ powder. The photocatalytic activity of the $TiO_2$ powder before and after APDBD treatment was evaluated by the degradation of methylene blue (MB) in aqueous solution. The apparent reaction rate constant of photolysis of the first sample of reused $TiO_2$ cleaned by APDBD improved to a level up to 0.32h-1 higher than the 30 % value of the initial $TiO_2$ powder. As the number of photolysis reactions and APDBD cleanings increased, the apparent rate constants gradually decreased; however, the fourth photolysis reaction still showed a value that was greater than 10% of the initial value. In addition, APDBD treatment enhanced the process by which $TiO_2$ effectively adsorbed MB at every photolysis stage.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2012년도 제42회 동계 정기 학술대회 초록집
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• pp.264-264
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• 2012

As an environment-friendly alternative energy resource, ethanol may be used to obtain hydrogen, a clean energy source. Thus, studies on catalytic reactions involving ethanol have been studied to understand the underlying principles in the reaction mechanism using various oxide-supported catalysts. Among them, Au-based catalysts have shown a superior activity in producing hydrogen gas. In the present study, Au/$TiO_2$ catalysts were prepared by deposition-precipitation method to understand their catalytic activities toward ethanol and acetaldehyde with increasing gold loading, especially at the very low Au loading regime. A commercially available $TiO_2$ (Degussa P-25) was employed and the Au loading was varied to 0, 0.1, 0.5, and 1.0 wt% respectively. The catalysts showed characteristic x-ray diffraction (XRD) features at $2{\theta}=78.5^{\circ}$ that could be assigned to the presence of gold nanoparticles. Its reactivity measurements were performed under a constant flow of ethanol and acetaldehyde at a flow rate of ${\sim}0.6{\mu}mol/sec$ and the substrate temperature was slowly raised at a rate of 0.2 K/sec. We observed that the overall reactivity of the catalysts increased with increasing Au loading along with selectivity favoring dehydrogenation to product hydrogen gas. In addition, we disclosed various reaction channels involving competitive reaction paths such as dehydrogenation, dehydration, and condensation. In addition, subsequent reactions of acetaldehyde obtained from dehydrogenation of ethanol, were found to occur and produce butene, crotonaldehyde, furan, and benzene. Based on the results, we proposed overall reaction pathways of such reaction channels.

• 한국응용과학기술학회지
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• 제8권2호
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• pp.161-167
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• 1991

The kinetics of hydrolysis of cinnamenylisophorone derivatives (${rho}-H,\;{rho}-Br,\;P-Cl,\;{rho}-OCH_3$) was investigated using ultraviolet spectrophotometry in 20%(v/v) dicxane-$H_2O$ at 25$^{\circ}C$. A rate equation which can be applied over wide pH range (pH $1.0{\sim}13.0$) was obtained. In order to investigate the substituent effects on cinnarnenylisophorone derivatives, Hammett constant was plotted. As the result, the rate of hydrolysis of cinnamenylisophorone derivatives was facilitated by electron donating group. Final products of the hydrolysis were benzaldehyde and isophorone, From the measurement of reaction rate constant according to pH changes, substituent effect, and final products, it was found that the hydrolysis of cinnarnenylisophorone derivatives was initiated by the neutral $H_2O$ molecule which does not dissociated at below pH 9.0, and in the range of pH $9.0{\sim}11.0$ this reaction occurs by $H_2O$ or hydroxide ion competitively, but proceeded by the hydroxide ion above pH 11.0. On the basis of this kinetic study, the reaction mechanism of the hydrolysis of cinnamenylisophorone derivatives was proposed.