• Bulletin of the Korean Chemical Society
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• 제14권4호
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• pp.457-461
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• 1993

Bioconcentration factors (BCF) in fish of organic nonelectrolytes are well correlated by a linear solvation energy relationship (LSER) of the form : log BCF= -0.95 + 4.74 $V_I/100 - 4.39{\beta} + 0.88{\alpha}$ where $V_I$ is the intrinsic solute molecular volume and ${\beta}$ and ${\alpha}$ are the solvatochromic parameters that measure hydrogen bond acceptor basicity and donor acidity of the compound. The LSER model can not only correlate the property with an accuracy comparable to molecular connectivity model but also provide a quantitative informationon on the nature and relative strength of solute-target system interactions affecting the property of interest. Such an information can hardly be obtained from molecular connectivity model.

• 대한화학회지
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• 제28권4호
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• pp.210-216
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• 1984

MeOH-MeCN 혼합용매의 Taft용매 파라미터인 ${\pi}^{\ast}$(용매의 polarity-polarizability), ${\alpha}$(용매의 수소결합 주게 산도) 그리고 ${\beta}$(용매의 수소결합 받게 염기도)를 여러 지시약을 사용하여 분광용매화 비교법으로 구하였다. 또한 Swain의 용매 파라미터인 A(음이온을 용매화 시키는 척도)와 B(양이온을 용매화 시키는 척도)를 반응속도 자료를 이용하여 최소 자승법으로 구하였다. 용매 상수 ${\beta}$는 용매의 염기도에 의존하며 혼합용매의 MeOH 함량이 증가할 수록 $(MeOH)_n$의 기여에 의해 증가하는 것을 알 수 있었다. ${\pi}^*$는 용매의 쌍극자 모멘트에 의존하며 혼합용매의 MeCN 함량이 증가할 수록 ${\pi}^{\ast}$값도 커지며 ${\alpha}$는 MeOH의 수소결합주게 효과에 의해 혼합용매의 MeOH함량이 증가할 수록 크게 증가하는 것을 나타냈다. 앞서 보고된 반응들에 용매 파라미터를 적용하여 반응상수를 구하였으며 Taft의 반응상수 a, s와 Swain의 반응상수 a, b사이에는 용매 척도의 차이 때문에 서로 연관성이 없었다. 그러나 그들의 비인 a/s와 a/b는 서로 좋은 직선관계를 보여 주었으며 이들 반응상수 비를 이용하여 반응 메카니즘이나 치환기 변화 및 이탈기 변화에 미치는 용매효과를 논의 하였다.

• Tribology and Lubricants
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• 제17권2호
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• pp.146-152
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• 2001

Environmentally adapted synthetic base oils of polyalkylene glycols (PAGs) and polyol esters (POEs) show a high polarity because of their functional groups containing oxygen atom. The lubricating performance of these polar base oils was investigated by using a four-ball tribometer under boundary lubrication condition. Four polyalkylene glycols and five polyol ester base oils were used as sample base oils of high polarity. A mineral oil (MO) and alkylnaphthalene (AN) were used as low polarity base oils. Tricrecylphosphate (TCP) was added to all the base oils, in the range of 10 mmol/L-2000 mmol/L, as an antiwear additive. All the TCP-for-mutated base oils showed optimum concentration characteristics for minimizing wear. The order of optimum concentration of all the base oils was in a good accordance with the order of relative stability of TCP in base oils. The interaction model on solvation between additive and different polar base oils can expect the stability order of TCP. Thus, the model on solvation can explain well the order of optimum concentration of all the base oils, by using the effect of polarity (dielectric constant, $\varepsilon$) and molecular size (molecular weight, MW) of them on stability of TCP in polar base oils. Finally, a good correlation of the optimum concentration for all the base oils was obtained when it was arranged as a function of C∝(M $W_{Base Oil}$/M $W_{TCP}$)$^{-2}$.71/.($\varepsilon$$_{Base Oil}$)$^{3.38}$ by these two parameters.s..

• 대한화학회지
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• 제36권3호
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• pp.345-350
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• 1992

Ln$(NO_3)_3$/DMF 상자성 용액의 양성자 선-나비와 화학적이동을 240 K부터 380 K 사이에서 측정하였다. 이들 데이터로부터 DMF 분자의 CHO기에 대한 배위구 교환속도와 열역학 교환파라미터를 추출하였다. 1/$T_2$ 와 ${\Dellta}{\omega}$ 데이터의 온도의존성을 자세하게 분석하고 고찰하여 결과를 정리하였다. 분석의 결과를 살펴보면 짝짓지 않은 전자 스핀이 몇몇 $Ln^{3+}$이온에서 첫 배위구를 넘어 퍼지면서 bulk 용매의 DMF 분자로 스칼라이완의 기여를 제공하는 것 같다.

• Bulletin of the Korean Chemical Society
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• 제33권8호
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• pp.2683-2688
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• 2012

The position of the thermodynamic equilibrium for reverse thermochromic spiropyran 6-carboxylates (SP-COOHs) was easily determined in aqueous binary mixtures, such as water-methanol, water-acetonitrile and water-dimethyl sulfoxide. The existence of more than one type of interconvertible species of the ring-opened form of SP-COOH in aqueous binary solvents enables us to evaluate the molar extinction coefficients of the ring-opened species of SP-COOH and to obtain the thermodynamic parameters.

• 대한화학회지
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• 제37권1호
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• pp.3-9
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• 1993

메탄올 및 에탄올 수용액내에서 1-adamantyl fluoroformate의 가용매분해반응속도를 여러 압력하에서 전도도방법을 이용하여 측정하였다. 이들 속도상수로부터 활성화부피(${\Delta}V^{\neq}{_o}$), 활성화압축율계수(${\Delta}{\beta}^{\neq}$), 활성화엔탈피(${Delta}H^{\neq}$), 활성화엔트로피(${Delta}S^{\neq}$), 그리고 활성화 착물에서의 charge development(△P)를 구하였다. 또한 에탄올 수용액내에서 가용매분해반응으로 인한 생성물에 대한 selectivity를 GC를 이용하여 측정하였다. 그 결과 ${\Delta}V^{\neq}{_o}$와 ${\Delta}{\beta}^{\neq}$의 값은 모두 음의 값을 ${Delta}H^{\neq}$는 양의 값을 ${Delta}S^{\neq}$은 큰 음의 값을 얻었다. 이 현상을 용매구조변화에 대하여 논의하였다. 이들 결과로부터 본 반응은 acyl carbon을 공격하는 이분자성반응과 가용매분해과정(S-D)인 용매-분리이온쌍반응으로 추정할 수가 있었다.

• Nuclear Engineering and Technology
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• 제6권1호
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• pp.23-26
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• 1974

염화 메탄 슬포닐의 할로겐 교환반응을 무수아세톤, 아세토니트릴, 메타놀 용매중에서 행하여 반응속도상수와 활성화파라메터를 구하였다. 친핵성도는 Cl->Br>I- 순서로 감소하였으며, 용매변화에 따른 염소이온과의 반응 속도는 ($CH_3$)$_2$CO>$CH_3$CN》$CH_3$OH의 순서로 감소하였다. 실험결과를 초기상태 탈용매화의 용이함과 천이상태 용매화의 안정성으로 설명하였다.

• Bulletin of the Korean Chemical Society
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• 제16권1호
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• pp.53-58
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• 1995

Heats of solution of aniline (AN), benzylamine (BA), ethyl-(EBS) and 2-phenylethyl benzenesulfonates (PEB) are calorimetrically measured in acetonitrile-methanol mixtures at 25.0 $^{\circ}C$. The activation parameters, ${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$ and ${\Delta}G^{\neq}$, are determined for the reactions of EBS and PEB with AN and BA using the kinetic data at three temperatures. Calorimetric transfer enthalpies of initial state, ${\delta}H_t^{0{\rightarrow}x})$(IS), and kinetically derived activation enthalpies, ${\delta}\;{\Delta}H^{\neq}$, in the MeCN-MeOH mixtures are combined to determine the transfer enthalpies of transition state, ${\delta}H_t^{0{\rightarrow}x})$(TS); ${\delta}H_t^{0{\rightarrow}x})$(IS) = ${\delta}{\Delta}H^{\neq}\;+\;{\delta}H_t^{0{\rightarrow}x}$(IS) The preferential solvation of anionic charge in the TS predicts a loose TS with a greater degree of bond cleavage for the reactions of PEB than for EBS, and also for the reactions with BA compared to the reactions with AN.

• Bulletin of the Korean Chemical Society
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• 제5권3호
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• pp.112-117
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• 1984

The association constants (K) of 3,5,N-trimethyl pyridinium iodide in 95 volume percent ethanol-water mixed solvent were determined by a modified UV and conductance method at $25^{\circ},\;30{\circ},\;40{\circ}\;and\;50{\circ}C$ over the pressure range 1 to 2000 bars. The association process is enhanced with increasing pressure and decreasing temperature. From K values, we obtained the total partial molar volume change (${\Delta}V$) and some thermodynamic parameters. The electrostriction volume (${\Delta}V_{el}$) and intrinsic volume (${\Delta}V_{in}$) were also evaluated. The values of ${\Delta}V,\;{\Delta}V_{el},\;{\Delta}V_{in}$ are negative, negative and positive, respectively, and the absolute values of all these three decrease with increasing pressure and temperature. The ion-pair size (a) were varied 3 to 6 ${\AA}$, with pressure and temperature. The solvation number (n) decreased from 2 to 0.5 with increasing temperature.

• Bulletin of the Korean Chemical Society
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• 제4권3호
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• pp.115-119
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• 1983

The ionic association constants (K) of 2, N-dimethyl pyridinium iodide (2NDMPI) in 95 volume percentage ethanol-water mixture were determined by a modified UV and conductance method at $20^{\circ}C{\sim}50^{\circ}C$ under 1 to 2000 bars. The K values increase with increasing pressure and decrease with temperature. The total partial molar volume change (${\Delta}V$) has relatively small negative value and the absolute ${\Delta}V$ value decrease with increasing pressure and temperature. The ion size (a) and solvation number (n) of 2NDMPI were about 5 $\AA$ and changed from 1 to 3 with decreasing temperature. Other thermodynamic parameters such as enthalpy (${\Delta}H^{\circ}$) and entropy (${\Delta}S^{\circ}$) for the equilibrium of the 2NDMPI were evaluated. From all the parameters mentioned above, we came to conclusion that the electrostriction effect of 2NDMPI in the ethanol-water mixture is enhanced with increasing pressure and decreasing temperature.