• 멤브레인
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• 제21권1호
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• pp.46-54
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• 2011

자연유기물을 처리하는 침지형 중공사막 정밀여과 시스템에서 $TiO_2$ 나노입자와 UV를 이용한 광촉매 반응을 적용 시 공기폭기, $TiO_2$ 농도, 용액의 pH 그리고 $Ca^{+2}$의 존재가 자연유기물에 의한 파울링에 미치는 혼합영향을 관찰하였다. 실험결과, $TiO_2$ 나노입자 없이 단순 UV의 조사만으로 자연유기물에 의한 파울링은 약 40% 정도 감소시킬 수 있었다. 또한 UV의 조사 없이 $TiO_2$ 나노입자의 교반만으로 약 25%의 파울링 감소효과를 나타내었다. 공기폭기가 광촉매 반응에 미치는 영향을 확인해 본 결과 공기폭기를 적용해 주지 않은 경우와 비교했을시 공기폭기로 인한 자연유기물의 제거효율은 약 12% 정도 향상되었다. 이는 공기폭기로 인한 분리막 표면으로부터 자연유기물의 물리적인 역수송 보다는 산소공급으로 인해 광촉매 반응이 더욱 향상된 것으로 판단된다. 공기폭기 유량, $TiO_2$ 농도, 용액의 pH 영향정도를 관찰한 결과 공기폭기가 자연유기물 파울링 감소에 미치는 영향이 가장 낮은 것으로 나타났다. 반면, 용액의 pH 경우 낮은 pH (= 4.5)에서 파울링 감소에 미치는 영향이 가장 높은 것으로 관찰되었다. 또한 $TiO_2$ 나노입자 농도가 증가할 수록 파울링 감소효과도 증가하였으며 용액의 pH를 낮출수록 파울링 감소는 증가하였다. 이는 낮은 pH에서 서로 반대전하를 지닌 자연유기물과 $TiO_2$ 나노 입자간의 정전기적인 인력이 증가하여 $TiO_2$ 나노입자 표면에서 자연유기물의 광촉매분해능이 향상된 것으로 사료된다. 또한 자연유기물 중 $Ca^{+2}$의 첨가는 상대적으로 높은 pH (= 10)에서 자연유기물과 $TiO_2$ 나노입자 사이 가교현상을 촉진시켜 $Ca^{+2}$이 첨가되지 않은 경우와 비교시 높은 파울링 감소효과와 자연유기물의 분해효과를 달성시킬 수 있었다.

• 한국분말재료학회지
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• 제13권4호
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• pp.243-249
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• 2006

Yttrium aluminum garnet (YAG) powders were synthesized via mechanochemical solid reaction using $Y_2O_3$ with three types of aluminum compounds. $Y_2O_3$ reacted mechanochemically with all A1 compounds and formed YAM (yttrium aluminum monoclinic), YAG and YAP (yttrium aluminum perovskite) phases depending on the starting materials. The ground samples containing ${\gamma}-A1_2O_3$ showed the best reactivity, whereas the ground sample containing A100H, which had the largest surface area, exhibited pure YAG after calcination at $1200^{\circ}C$. The sample containing Al had the least reactivity, producing YAP along with YAG at $1200^{\circ}C$. The types and grinding characteristics of the starting materials and grinding time are believed to be important factors in the mechanochemical synthesis of YAG.

• Bulletin of the Korean Chemical Society
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• 제29권3호
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• pp.585-589
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• 2008

Second-order rate constants (kN) have been measured for reactions of Y-substituted phenyl 2-thiophenecarboxylates (6a-h) with morpholine and piperidine in 80 mol % H2O/20 mol % DMSO at 25.0 0.1 oC. The Brnsted-type plot for the reactions of 6a-h with morpholine is linear with b lg = 1.29, indicating that the reactions proceed through a tetrahedral zwitterionic intermediate (T?). On the other hand, the Brnsted-type plot for the reactions of 6a-h with piperidine exhibits a downward curvature, implying that a change in the rate-determining step occurs on changing the substituent Y in the leaving group. Dissection of kN into microscopic rate constants (i.e., k1 and k2/k1 ratio) has revealed that k1 is smaller for the reactions of 6a-h than for those of Y-substituted phenyl 2-furoates (5a-h), while the k2/k1 ratio is almost the same for the reactions of 5a-h and 6a-h. It is also reported that modification of the nonleaving group from the furoyl (5a-h) to the thiophenecarbonyl (6a-h) does not influence pKao (defined as the pKa at the center of the Brnsted curvature) as well as the k2/k1 ratio.

• 약학회지
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• 제19권4호
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• pp.219-226
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• 1975

Physical and chemical properties on the aging inhibition mechanism of hydrous aluminum oxide were studied by means of dehydration velocity, activation energy, DTA, TGA, IR spectra, X-ray diffraction and TMA. During aging, changes may occur in the hydrous aluminum oxide structure which results in a loss of acid reactivity and in crystal formation to the hydrated hydrous alumina. The results obtained from the X-ray diffraction pattern and DTA, TGA thermogram studies showed that the aging product stabilized with either sorbitol or mannitol was hydrous aluminum oxide ($Al_{2}O_{3}{\cdot}xH_{2}O$) but the aging product not stabilized with either sorbitol or mannitol product not stabilized was hydrated hydrous aluminum oxide $Al_{2}O_{3}{\cdot}xH_{2}O{\cdot}yH_{2}O$. The activation energy of dehydration of the hydrous almina was about 17 Kcal. mol$^{1}$ deg$^{-1}$ which was observed a little less than that of 22 kcal.mol.$^{-1}$ deg.$^{-1}$ of or mannitol, the inhibition mechanism in the aging process from oxide is assumed to prevent the formation of the hydrated hydrous aluminum oxide and the aging process is thought of as analogous to the polymorphic transformations which occur as a system converts to its most stable state.

• Bulletin of the Korean Chemical Society
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• 제28권2호
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• pp.220-224
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• 2007

Second-order rate constants (kN) have been determined spectrophotometrically for reactions of 2,4-dintrophenyl 2-furoate (2) with a series of alicyclic secondary amines in 80 mol % H2O/20 mol % dimethyl sulfoxide (DMSO) at 25.0 oC. The furoate 2 is more reactive than 2,4-dintrophenyl benzoate (1) toward all the amines studied. The higher acidity of 2-furoic acid (pKa = 3.16) compared with benzoic acid (pKa = 4.20) has been suggested to be responsible for the reactivity order, at least in part. The Brønsted-type plots for the reactions of 1 and 2 are curved downwardly, indicating that the aminolyses of both 1 and 2 proceed through a zwitterionic tetrahedral intermediate (T±) with a change in the rate-determining step on changing the amine basicity. Dissection of the kN values into their microscopic rate constants has revealed that the pKao and k2/k-1 ratios for the reactions of 1 and 2 are identical, indicating that the nature of the nonleaving group (i.e., benzoyl and 2-furoyl) does not affect the reaction mechanism. The k1 values have been found to be larger for the reactions of 2 than for those of 1, which is fully responsible for the fact that the former is more reactive than the latter.

• 한국작물학회지
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• 제47권1호
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• pp.54-61
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• 2002

The antioxidant activities of methanol extracts of sixteen samples were tested using 1.1-diphenyl-2-picryl hydrazyl(DPPH) reactivity and TBARS substances assay in vitro. The methanol extracts of the rice brans from three wild rice -O. minuta, O. rufipogon, and O. barthii-were found to be the most effective in DPPH radical scavenging activity. The next effective ones were the rice brans of Heugjinjubyeo and leaves of Tapgolbori. When tested on lipid peroxidation using a lipid peroxidation generation system mediated by $H_2O$$_2$/Fe$^{2+}$ in rat liver homogenates, the brans and hull of wild rice (O. minuta, O. rufipogon, and O. barthii) and rice bran of Heugjinjubyeo exhibited protective activities against lipid peroxidation in the order of effectiveness.s.

• Bulletin of the Korean Chemical Society
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• 제28권8호
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• pp.1353-1357
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• 2007

Second-order rate constants (kN) have been determined spectrophotometrically for reactions of Y-substituted phenyl 2-furoates (1a-h) with piperidine and morpholine in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 oC. The Brønsted-type plot exhibits a downward curvature for the reactions with strongly basic piperidine but is linear for the reactions with weakly basic morpholine. The slope of the curved Brønsted-type plot changes from -1.25 to ?0.28 as the pKa of the conjugate acid of the leaving aryloxides decreases. The pKa at the center of the Brønsted curvature, defined as pKa°, was determined to be 6.4. The aminolysis of 1a-h has been concluded to proceed through a stepwise mechanism on the basis of the curved Brønsted-type plot. The reactions of Ysubstituted phenyl cinnamates (2a-g) with piperidine resulted in a curved Brønsted-type plot with a pKa° values of 6.4. However, the curved Brønsted-type plot has been suggested to be not due to a change in the RDS but due to a normal Hammond effect of a concerted mechanism, since the Brønsted-type plot for the corresponding reactions with morpholine results in also a curved Brønsted-type plot with a pKa° values of 6.1. The furoates with a basic leaving group (i.e., 1b-g) are less reactive than the corresponding cinnamates (i.e., 2b-g). The k2/ k-1 ratios for the reactions of 1b-h are much smaller than unity, which has been suggested to be responsible for their low reactivity.

• Bulletin of the Korean Chemical Society
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• 제15권2호
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• pp.126-132
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• 1994

RhCl [P($C_6H_5)_3]_3$ complexes have been incorporated in polysulfone (PS) as a dispersion medium using cosolvent (THF). The interactions between Rh(Ⅰ) complexes and polysulfone polymer molecules are examined by infrared spectroscopy and thermal analysis. The chemical reactivity of Rh in PS films has been investigated by reacting Rh sites with CO, $H_2,\;D_2,\;O_2\;NO,\;C_2H_2\;and\;C_2H_4$ in the temperature range $25-200^{\circ}C$. Various Rh-carbonyl, -hydride and -nitrosyl species formed in PS films are characterized by their infrared spectra. Rh complexes in PS film show interesting catalytic reactivities in the reactions such as hydrogenation of $C_2H_2\;and\;C_2H_4$, oxidation of CO, and reduction of NO by CO or $H_2$ gas under relatively mild conditions.

• Bulletin of the Korean Chemical Society
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• 제31권7호
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• pp.1915-1919
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• 2010

Second-order rate constants $(k_N)$ have been measured for reactions of 2,4-dinitrophenyl phenyl carbonate (2) with a series of pyridines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$ and compared with the $k_N$ values reported for the corresponding reactions of 2,4-dinitrophenyl benzoate (1) to investigate the effect of nonleaving group on reactivity and mechanism. The reactions of 2 result in larger $k_N$ values than those of 1. The Br${\o}$nsted-type plot for the reactions of 2 exhibits a downward curvature (i.e., ${\beta}2$ = 0.84 and ${\beta}1$ = 0.16), which is typical for reactions reported to proceed through a stepwise mechanism with a change in rate-determining step. The $pK_a$ at the center of the Br${\o}$nsted curvature, defined as $pK_a{^{\circ}}$, has been found to be 8.5 and 9.5 for the reactions of 2 and 1, respectively. Dissection of $k_N$ into the microscopic rate constants (e.g., $k_1$ and $k_2/k_{-1}$ ratio) has revealed that the reactions of 2 result in larger k1 values than those of 1, indicating that PhO behaves as a stronger electron-withdrawing group than Ph. However, the $k_2/k_{-1}$ ratio has been found to be independent of the electronic nature of Ph and PhO.

• 청정기술
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• 제2권1호
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• pp.69-79
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• 1996

석탄가스화기에서 방출되는 황을 제어하는 것은 가스정화시스템에서 연료가스 중의 황화수소를 제거하는 것이다. 이에 본 연구에서는 천연산 망간광석의 황화수소 제거능에 영향을 미치는 탈황제의 입자크기, 황화반응 온도 및 탈황제 특성에 대해서 고찰하였다. 실험결과 황화수소 제거능은 반응온도 $700^{\circ}C$에서 효과적이었으며 입자크기가 작을수록 탈황효율은 증가하였으나 그 차이는 크지 않았다. 온도가 증가할수록 탈황제의 응집으로 인해 입자 내 물질전달저항이 증가하여 반응성이 저하되며 SEM 사진으로 탈황제의 응집을 확인할 수 있었다. 실험으로부터 구한 평형비 ($P_{H_2O}/P_{H_2S}$)는 ${\log}(P_{H_2O}/P_{H_2S})=5653/T-3.7909$였다. 천연산 망간광석의 황화수소 제거능이 기존에 개발되어 있는 탈황제들과 비슷하기 때문에 탈황제로 사용할 수 있음을 알았다.