• Title/Summary/Keyword: Steric Hindrance

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Cooling and Antisolvent Crystallization of Potassium Bicarbonate in the Presence of Sterically Hindered Alkanolamines (입체 장애 알카놀아민 혼합 수용액에서 중탄산칼륨 결정의 냉각 반용매 결정화)

  • Jo, Chang Sin;Jung, Taesung;Yoon, Hyoung Chul;Kim, Jong-Nam;Rhee, Young Woo
    • Clean Technology
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    • v.20 no.4
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    • pp.383-389
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    • 2014
  • $CO_2$ absorption processes have a good potential for large scale capture of $CO_2$ but a large amount of absorbing solution has to be regenerated, undesirably increasing the consumption of energy such as sensible heat and latent heat of vaporization. In this study, a cooling crystallization process which would separate the $CO_2$-rich potassium bicarbonate crystals from $CO_2$-lean water was developed to reduce the energy penalty. Sterically hindered alkanolamine additives were used to enhance the $CO_2$ removal efficiency and their antisolvent effect on the crystallization was found in a continuous cooling crystallizer. The production yields of crystals were increased in the sequence of 2-amino-2-methyl-1-propanol (AMP) < 2-amino-2-methyl-1,3-propanediol (AMPD) < 2-amino-2-hydroxymethyl-1,3-propanediol (AHPD), which are related to the number of hydroxyl groups in the additive molecules. Using $^{13}carbon$ nuclear magnetic resonance, the additives favored the formation of bicarbonate ions by steric hindrance effect and increased the supersaturation of $KHCO_3$. It is shown that the additives increase the mean size of crystals and crystal growth rate by increasing supersaturation. The additives are promising for enhancing the $CO_2$ removal efficiency and reducing the regeneration energy cost of $CO_2$ absorbing solution by promoting $KHCO_3$ crystallization.

Comparison of the Hydrolysis Rate of Several Polyol Ester Oils as a Candidate for Environmentally Adapted Synthetic Base Oil (환경친화적인 합성기유 후보물질로서의 몇가지 폴리올에스터 오일의 가수분해속도 비교)

  • 한두희;마사부미마스꼬
    • Proceedings of the Korean Society of Tribologists and Lubrication Engineers Conference
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    • 2001.06a
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    • pp.162-177
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    • 2001
  • The hydrolysis rates of seven kinds of polyol ester base oils 〔POEs〕 of different branch shape were investigated by using a simple apparatus under mild acidic condition. Seven polyol ester base oils were made of poly hydric alcohols of two-four valence, normal or branched fatty acids of different carbon number. p-Toluene sulfonic acid was used as acid catalyst to accelerate the rate of hydrolysis. Partial esters and fatty acid produced by sequential hydrolysis of POEs were identified and their concentrations were determined by calibrated-internal standard method using Gas Chromatography. The rate constants of each step in sequential hydrolysis were determined by the least square method from rate equation and the concentration of each component, were compared with one another. It was shown that the rate of hydrolysis of POEs was strongly affected by whether molecular structure of fatty acid was straight chain or branch chain and which position was branched. The hydrolysis stability for all the POEs can be reasonably explained by using a steric hindrance effect anticipated fi:om their molecular structures affecting as water molecule makes an attack on the carbonyl carbon of POEs.

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Synthesis and Characterization of Reactive Liquid Crystalline Compounds with Azo-mesogenic Groups at the 4-, 3,5-, or 3,4,5-Positions of Phenyl Ring (페닐고리의 4-, 3,5-, 또는 3,4,5-위치에 아조-메소젠기를 갖는 반응성 액정화합물의 합성 및 특성)

  • Park, Jong-Ryul;Yoon, Doo-Soo;Bang, Moon-Soo
    • Applied Chemistry for Engineering
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    • v.30 no.2
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    • pp.247-253
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    • 2019
  • In this study, compounds with azo-mesogenic groups at 4-, 3,5-, or 3,4,5-positions of one phenyl ring were synthesized, and their liquid crystallinity and photochemistry were investigated. The compounds in the Azo1 and Azo2 series had linear and planar geometries, respectively, while those in the Azo3 series had relatively bulky structures. Compounds of BA-Azo2 and BA-Azo3 did not show any liquid crystallinity. Compounds of BE-Azo1 and BE-Azo2 exhibited a monotropic liquid crystallinity, while the other compounds showed an enantiotropic liquid crystallinity. The liquid crystalline behavior was imparted by the azo-mesogenic groups, and most of the liquid crystalline compounds formed a smectic phase. All the RM-AzoX compounds exhibited photoisomerism because of the presence of the azo groups in the molecule. The rate of photoisomerization followed the order of RM-Azo3 < RM-Azo1 < RM-Azo2 and was considered to depend on the steric hindrance around the azobenzene groups in the molecule. These results suggest that the liquid crystallinity and photochemical property of the compounds are affected by the position or the number of azo-mesogenic groups phenyl ring of the molecule.

Chemical Reactions in Surfactant Solutions (II). Nucleophilic and Micellar Catalyses of Sodium 2-Alkylbenzimidazole-5-sulfonates on Hydrolyses of Carboxylic Esters in Aqueous and CTABr Solutions (계면활성제 용액속에서의 화학반응 (제 2 보). 카르복시산 에스테르의 가수 분해 반응에 미치는 2-알킬벤즈이미다졸-5-술포네이트의 친핵적 및 미셀효과)

  • Young Seuk Hong;Jeung Bae Kim;Hee Hyun Park;Dae Ryong Lee
    • Journal of the Korean Chemical Society
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    • v.33 no.1
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    • pp.97-105
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    • 1989
  • This study deals with micellar effects on hydrolyses of p-nitrophenyl carboxylic esters(p-NPCE) mediated by 2-alkylbenzimidazole(R-BI) and sodium 2-alkylbenzimidazole-5-sulfonate(R-BISO$_3$Na) in aqueous and CTABr solutions. The reactions mediated by R-BI and R-BISO$_3$Na in micellar solutions are obviously slower than those by benzimidazole(BI) and sodium benzimidazole-5-sulfonate(BISO$_3$Na) respectively, and the reaction rates were decreased with increase of lengths of alkyl groups. This prestents a striking contrast to the reactions in aqueous solutions without added CTABr, of which the reaction rates are on approximately same levels. It seems due to steric effect of alkyl groups for R-BI and R-BISO$_3$Na in the Stern layer of micelle, and it is supported by measured activation parameters(${\Delta}H^{\neq},\;{\Delta}G^{\neq}\;and\;{\Delta}S^{\neq}$) of the reactions in aqueous and micellar solutions. In addition to nucleophilic ability of benzimidazole(BI) moiety of R-BISO$_3$Na on the reactions, these compounds with long alkyl groups(nonyl to pentadecyl) which form a micelle of themselves increase the reaction rates due to their micellar catalyses in aqueous solutions, not including CTABr. We measured the isotope effects to elucidate the mechanism of hydrolyses of p-nitrophenyl carboxylic esters, and the relative first order rate constant($k'_{H_2O}/k'_{D_2O}$) are on range of 2.5∼3.2. This range is too high to conclude that the hydrolyses of p-NPA mediated by various R-BISO$_3$Na proceed by nucleophilic mechanism. In other words, the reactions are assumed to proceed in part by general basic one, as compared with the reaction catalyzed by imidazole(IM) in aqueous solution.

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Multivessel Coronary Revascularization with Composite LITA-RA Y Graft (좌내흉동맥-요골동맥 복합이식편을 이용한 다중혈관 관상동맥우회술)

  • Lee Sub;Ko Mgo-Sung;Park Ki-Sung;Ryu Jae-Kean;Jang Jae-Suk;Kwon Oh-Choon
    • Journal of Chest Surgery
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    • v.39 no.5 s.262
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    • pp.359-365
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    • 2006
  • Background: Arterial grafts have been used to achieve better long-term results for coronary revascularization. Bilateral internal thoracic artery (ITA) grafts have a better results, but it may be not used in some situations such as diabetes and chronic obstructive pulmonary disease (COPD). We evaluated the clinical and angiographic results of composite left internal thoracic artery-radial artery (LITA-RA) Y graft. Material and Method: Between April 2002 and September 2004, 119 patients were enrolled in composite Y graft for coronary bypass surgery. The mean age was $62.6{\pm}8.8$ years old and female was 34.5%. Preoperative cardiac risk factors were as follows: hypertension 43.7%, diabetes 33.6%, smoker 41.2%, and hyperlipidemia 22.7%, There were emergency operation (14), cardiogenic shock (6), left ventricle ejection fraction (LVEF) less than 40% (17), and 17 cases of left main disease. Coronary angiography was done in 35 patients before the hospital discharge. Result: The number of distal anastomoses was $3.1{\pm}0.91$ and three patients (2.52%) died during hospital stay. The off-pump coronary artery bypass (OPCAB) was applied to 79 patients (66.4%). The LITA was anastomosed to left anterior descending system except three cases which was to lateral wall. The radial Y grafts were anastomosed to diagonal branches (4), ramus intermedius (21), obtuse marginal branches (109), posterolateral branches (12), and posterior descending coronary artery (8). Postoperative coronary angiography in 35 patients showed excellent patency rates (LITA 100%, and RA 88.5%; 3 RA grafts which anastomosed to coronary arteries <70% stenosed showed string sign with competitive flow). Conclusion: The LITA-RA Y composite graft provided good early clinical and angiographic results in multivessel coronary revascularization. But it should be cautiously used in selected patients.