• 제목/요약/키워드: SOLVENT EFFECT

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Kinetic Studies of the Solvolyses of 2,2,2-Trichloro-1,1-Dimethylethyl Chloroformate

  • Koh, Han-Joong;Kang, Suk-Jin;Kevill, Dennis N.
    • Bulletin of the Korean Chemical Society
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    • 제31권4호
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    • pp.835-839
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    • 2010
  • The rate constants of solvolyses of 2,2,2-trichloro-1,1-dimethylethyl chloroformate ($\underline{I}$) in 33 solvents can be well correlated using the extended Grunwald-Winstein equation, with incorporation of the $N_T$ solvent nucleophilicity scale and the $Y_{Cl}$ solvent ionizing scale, with sensitivities towards changes in the scale having values of $1.42\;{\pm}\;0.09$ for l and $0.39\;{\pm}\;0.05$ for m, respectively. The activation enthalpies are ${\Delta}H^{\neq}\;=\;12.3$ to $14.5\;kcal{\cdot}mol^{-1}$ and the activation entropies are -28.2 to $-35.5\;cal{\cdot}mol^{-1}{\cdot}K^{-1}$, consistent with the proposed bimolecular reaction mechanism. The kinetic solvent isotope effect of 2.14 in MeOH/MeOD is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

Polymer Dielectrics and Orthogonal Solvent Effects for High-Performance Inkjet-Printed Top-Gated P-Channel Polymer Field-Effect Transistors

  • Baeg, Kang-Jun;Khim, Dong-Yoon;Jung, Soon-Won;Koo, Jae-Bon;You, In-Kyu;Nah, Yoon-Chae;Kim, Dong-Yu;Noh, Yong-Young
    • ETRI Journal
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    • 제33권6호
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    • pp.887-896
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    • 2011
  • We investigated the effects of a gate dielectric and its solvent on the characteristics of top-gated organic field-effect transistors (OFETs). Despite the rough top surface of the inkjet-printed active features, the charge transport in an OFET is still favorable, with no significant degradation in performance. Moreover, the characteristics of the OFETs showed a strong dependency on the gate dielectrics used and its orthogonal solvents. Poly(3-hexylthiophene) OFETs with a poly(methyl methacrylate) dielectric showed typical p-type OFET characteristics. The selection of gate dielectric and solvent is very important to achieve high-performance organic electronic circuits.

Rate and Product Studies on the Solvolyses of Allyl Chloroformate

  • Koh, Han Joong;Kang, Suk Jin
    • Bulletin of the Korean Chemical Society
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    • 제33권12호
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    • pp.4117-4121
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    • 2012
  • The solvolysis rate constants of allyl chloroformate ($CH_2=CHCH_2OCOCl$, 3) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and $Y_{Cl}$ solvent ionizing scale, with the sensitivity values of $0.93{\pm}0.05$ and $0.41{\pm}0.02$ for l and m, respectively. These l and m values can be considered to support a $S_N2$ reaction pathway. The activation enthalpies (${\Delta}H^{\neq}$) were 12.5 to 13.4 $kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -34.4 to -37.3 $cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is also consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, $k_{MeOH}/k_{MeOD}$) of 2.16 was also in accord with the $S_N2$ mechanism. The values of product selectivity (S) for the solvolyses of 3 in alcohol/water mixtures was 1.3 to 3.9, which is also consistent with the proposed bimolecular reaction mechanism.

Effect of Dodecylbenzene Sulfonic Acid on the Behavior of Asphaltene Aggregation in a Solvent Deasphalting System

  • Liu, Lingyu;Go, Kang Seok;Nho, Nam Sun;Kim, Kwang Ho;Rhee, Young-Woo
    • Korean Chemical Engineering Research
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    • 제56권1호
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    • pp.14-23
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    • 2018
  • The effect of dodecylbenzene sulfonic acid (DBSA) with different addition amount of DBSA ($M_{DBSA}$), temperatures and solvent-to-oil ratio (SOR, v/v) on asphaltene aggregation in a solvent deasphalting system was investigated. Increasing the $M_{DBSA}$ at SOR 10 and $55^{\circ}C$ caused the asphaltene removal ratio (ARR) to increase first, then maximize at 1 wt% of $M_{DBSA}$ and then decrease continuously. Based on the SARA (saturate, aromatic, resin, asphaltene) composition, the adsorption amount of DBSA on the asphaltene surface and the self-aggregation of the DBSA, the reason for the change in ARR with $M_{DBSA}$ was found due to the adsorption mechanism. In addition, the asphaltene-resin-DBSA colloidal size confirmed the change of adsorption behavior between the asphaltene and DBSA. Based on the results of this study, a hypothetical adsorption mechanism of DBSA on asphaltene aggregation in the solvent deasphalting system was conceived of and proposed.

폴리에틸렌 왁스와 무수 말레인산의 그라프팅 중합 반응에서 용매가 미치는 영향 (Effect of Solvent on the Grafting Polymerization of Polyethylene Wax with Maleic anhydride)

  • 유시원;최중소;나재식
    • 자원리싸이클링
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    • 제23권1호
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    • pp.48-57
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    • 2014
  • 본 연구에서는 고밀도 폴리에틸렌 제조공정에서 부산물로 생성되는 폴리에틸렌 왁스를 대상으로 무수말레인산을 그라프트 반응 시킬 때, 반응 용매가 가지는 성질의 영향에 대해서 조사하였다. 측정결과, 자일렌이 톨루엔보다 우수한 모노머 용해성, 팽윤성, 혼화성을 가지며, 그라프트 반응을 더욱 촉진함을 알 수 있었고, 반응 용매의 함량에 따라서는 0 ~ 200% v/w영역에서 200% v/w 조건이 최대의 그라프트 율을 보이고, 그이상의 용매가 사용될 경우에는 그라프트 율이 다시 감소하다가 일정해짐을 확인하였다. 가교도 함량 값은 용매 존재 하에 거의 생성되지 않았으며, 용매가 용매분자로 사슬이동반응 시켜 가교반응을 방지하는 것으로 판단되었다. $140^{\circ}C$에서 측정된 용융 점도 값은 폴리에틸렌 왁스에 무수말레인산이 그라프트 된 후에 증가하는 경향을 보임을 알 수 있었다.

단일 및 혼합 용매계 실리카 분산체의 점도 특성 및 유변학적 거동 (The Rheology of the Silica Dispersion System with Single and Mixed Solvent)

  • 안재범;노시태
    • 공업화학
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    • 제20권6호
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    • pp.685-691
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    • 2009
  • 하이드록시기 유무, 극성도, 분자 크기가 서로 다른 용매 6종의 단일 용매 또는 혼합 용매계 흄드 실리카 분산체를 제조하고 각 분산체의 점도 및 유변학적 거동을 용매계의 특성의 관점에서 고찰하였다. 하이드록시기 포함 용매에 실리카를 분산하였을 때 안정적이고 저점도의 sol을 형성하였고 하이드록시기가 없고 비극성인 용매는 고점도의 gel을 형성하였다. 비극성 용매계 실리카 분산체에 하이드록시기 함유 용매를 첨가하면 일정 함량까지는 점도 감소 현상을 관찰할 수 있었으며, 더 이상의 점도 변화가 발생하지 않는 최소 임계함량이 있었다. 최소 임계함량은 하이드록시기 미포함 용매의 극성도가 클수록 줄어들었다. 하이드록시기 포함 용매계 실리카 분산체가 안정적인 저점도의 sol을 형성하는데 이는 실리카 표면의 실란올기와 용매의 하이드록시기간의 수소결합을 통한 용매화로 저점도 sol을 형성하는 것으로 볼 수 있다. 비극성용매에 실리카를 분산하였을 때는 실리카 표면의 실란올기 사이의 수소 결합을 통해 응집이 일어나 고점도의 gel이 형성되었다.

PTT 섬유의 염색성 (2) - 용제 처리한 PTT 섬유의 염색성 및 물성 - (Dyeing Properties of PTT Fiber (2) - Effect of Solvent Treatment on Dyeing and Physical Properties of PTT Fiber -)

  • 이두환;정동석;김호정;이문철
    • 한국염색가공학회지
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    • 제15권4호
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    • pp.8-16
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    • 2003
  • Poly(trimethylene terephthalate)(PTT) fiber was pretreated with organic solvent/water solution of various compositions. The organic solvents used in this experiment were benzyl alcohol, n-buthanol, and N,N-dimethylformamide(DMF). Density of the fibers were investigated as a measure of crystallite region. The dye uptake increased in the order of pretreatment with hot water < untreated < 5% benzyl alcohol < 100% benzyl alcohol < 90% benzyl alcohol; hot water < untreated $\risingdotseq$ 5% butanol < 100% beutanol < 90% butanol; hot water $\risingdotseq$ 5% DMF < untreated < 90% DMF < 100% DMF. The dye uptake increases with increase of crystallinity. It seems likely that the recrystallization process during the pretreatment with organic solvent/water solutions leads to an increase in the microvoid and then a large increase in the dye uptake. Also the dyeing rate increased and the dyeing transition temperature decreased with the pretreatments. The results obtained are corresponds with the plasticization of the fiber structure formed during the pretreatrnent.

Studies on Solvent Extraction Using Salphen for Separative Determination of Trace Fe(II) and Fe(III) in Water Samples

  • Kim, Eun-Jook;Kim, Young-Sang;Choi, Jong-Moon
    • Bulletin of the Korean Chemical Society
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    • 제29권1호
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    • pp.99-103
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    • 2008
  • Solvent extraction using salphen as a ligand has been investigated for the selective separation and determination of trace Fe(II) and Fe(III). A salphen ligand was synthesized, and solvent extraction variables, such as solution pH, the concentration of salphen, the type of organic solvent, auxiliary agents, oxidants and the effect of interference were optimized. Salphen is stable at pH 3-4, and Fe(III)-salphen complexes can be selectively extracted into an MIBK(4-methyl-2-pentanone) phase from an aqueous solution within this pH range. For the determination of the total amount of iron in 100 mL of aqueous solution, Fe(II) ions were completely oxidized using 0.05 mL of 3.5% H2O2 without side reactions. To evaluate its applicability, the proposed method was applied to determine trace Fe(II) and Fe(III) in several kinds of water samples. Reproducible results were obtained with RSD of less than 3.0%, and the recoveries for this reliability were obtained with 91-112%.

Effect of Solvent Extraction on the Anti-complementary Activities of Green and Ripe Cucurbita moschata Duch

  • Yang, Jin-Ok;Kim, Chang-Jin;Song, Kyung-Bin
    • Preventive Nutrition and Food Science
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    • 제6권2호
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    • pp.133-135
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    • 2001
  • The edible part of cucurbita moschata Duch, which is commonly used as a Korean traditional medicine as well as a popular food source, was studied to isolate anti-complementary substance. Extracts of Cucurbita moschata Duch showed significant anti-complementary activities on the classical pathway of the complement system. Especially, the ripe Cucurbita moschata Duch had more activity than that of the complement system. Especially, the ripe Cucurbita moschata Duch had more activity than that of the green one in terms of the overall anti-complementary activity. Among the extracts of various organic solvents of the ripe Cucurbita moschata Duch, chloroform and ethyl-acetate extracts, which are non-polar solvent extracts, showed the strongest activities. These results suggest that the major difference in the solvent extraction for the anti-complementary substances depends on the change in the chemical composition such as the fatty acid with the degree of ripening.

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치환염 벤조일과 파라니트로아닐린과의 친핵반응에 미치는 용매효과에 관한 연구 (Solvent Effect in Nucleophilic Reactions of Substituted Benzoyl Chlorides with p-Nitroaniline)

  • 김왕기
    • 대한화학회지
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    • 제18권4호
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    • pp.251-258
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    • 1974
  • 아세톤, 아세토니트릴, 메탄올, 에탄올 등의 용매에서 치환염 벤조일과 파라니트로아닐린과의 친핵치환반응에 대한 속도상수를 전기 전도도법으로 구하고 활성화 파라미터를 계산하였다. 결과로 반양성자 용매보다는 양성자성 용매에서 반응속도가 빨랐고 같은 성질의 용매에서는 유전상수가 큰 쪽이 반응이 더 빨랐으며 각 용매에 있어서의 Hammett도시는 정의 기울기를 가진 직선을 나타내었으며, 반응은 첨가-제거 메카니즘으로 일어났다.

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