• Bulletin of the Korean Chemical Society
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• 제34권1호
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• pp.49-53
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• 2013

Second-order rate constants have been measured spectrophotometrically for the reactions of phenyl Y-substituted-phenyl carbonates 7a-g with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The ${\alpha}$-nucleophile $Ox^-$ is 53-95 times more reactive than the corresponding normal-nucleophile 4-$ClPhO^-$ toward 7a-g, indicating that the ${\alpha}$-effect is operative. The magnitude of the ${\alpha}$-effect (e.g., the $k_{Ox^-}/k_{4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent Y. The cause of the ${\alpha}$-effect for the reactions of 7a-g has been suggested to be ground-state (GS) effect rather than transition-state (TS) stabilization through a six-membered cyclic TS, in which $Ox^-$ behaves a general acid/base catalyst. This idea is further supported by the result that $OH^-$ exhibits negative deviation from the linear Br${\o}$nsted-type plot composed of a series of aryloxides, while $Ox^-$ deviates positively from the linearity. Differential solvation of the GS of $Ox^-$ and 4-$ClPhO^-$ has been suggested to be responsible for the ${\alpha}$-effect exerted by $Ox^-$.

• Bulletin of the Korean Chemical Society
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• 제23권9호
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• pp.1263-1307
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• 2002

Pseudo-first-order rate constants (kobs) have been determined for the nucleophilic substitution reactions of p-nitrophenyl diphenyl phosphinate (PNPDPP) with substituted phenoxides (XC6H4O - ) and butane-2,3-dione monoximate (Ox- ) in 0.1 M borate buffer (pH = 10.0) at 25.0 ${\pm}0.1^{\circ}C$. The kobs value increases sharply upon addition of cethyltrimethylammonium bromide (CTAB) to the reaction medium up to near 7 ${\times}$ 10-4 M CTAB and then decreases smoothly upon further addition of CTAB. The rate enhancement upon the addition of CTAB is most significant for the reaction with -O2CC6H4O- and least significant for the one with C6H5O- , indicating that the reactivity of these aryloxides in the presence of CTAB cannot be determined by the basicity alone. The strength of the interaction of these anionic aryloxides with the positively charged micellar aggregates has been suggested to be an important factor to determine the reactivity in the presence of CTAB. The kobs value for the reaction with Ox- increases also upon the addition of CTAB. However, the increase in the kobs value is much more significant for the reaction with Ox- than for the one with ClC6H4O- , indicating that Ox- is less strongly solvated than ClC6H4O- in H2O. The ${\alpha}-effect$ shown by Ox- in H2O has been attributed to the ground-state solvation difference between Ox- and ClC6H4O- .

• 대한화학회지
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• 제24권6호
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• pp.444-451
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• 1980

극성용매에서 전자의 용매화과정을 구체적으로 고찰하여 보기 위하여 테트라히드로퓨란(THF)-물 이성분계의 메디움효과를 측정하였다. 이 메디움효과는 Pt|$H_2Q$, Q, HCI, THF, $H_2O$|KC1 | $Hg_2Cl_2$|Hg(Pt) 셀로 수용액과 다른 용액(TGF-$H_2O$)에서 결정된 $H^+$ 이온에 대한 자유에너지 변화의 차(${\Delta}{\Delta}G_0$)를 이용하여 연구하였다. 여기서 $H_2Q$와 Q는 히드로퀴논과 퀴논을 각각 나타낸다. 자유에너지 변화의 차와 용매화된 전자의 최대흡수 에너지에 대한 용매의 유전상수 영향을 고찰하기 위하여 THF에서 $H_2O$의 회합정도를 관찰하였다. $H_2O$의 회합정도는 $H_2O$의 근적외선 스펙트럼을 이용하여 분석하였다. 이들 실험결과로부터 이성분 혼합용매에서 전자나 다른 이온의 용매화는 용매의 특정성분과 선택적으로 진행된다는 것을 알았다.

• Bulletin of the Korean Chemical Society
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• 제29권8호
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• pp.1519-1524
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• 2008

We have investigated the photophysics of the acetone radical cation in the vacuum ultraviolet energy region by multiphoton ionization combined with time-of-flight mass spectrometry in a cluster beam. We have found that the loss of methyl radical from the acetone radical cations is remarkably suppressed at 10.5 eV when they are solvated by a few neutral acetone molecules. The cluster ion mass spectra obtained by nanosecond and picosecond laser pulses reveal that there are intermolecular processes, occurring in several tens of picoseconds, which are responsible for the survival of the acetone cations in clusters. This remarkable solvation effect on the yield of the methyl radical loss from the acetone cation can be rationalized by the intracluster vibrational energy redistribution and the self-catalyzed enolization which compete with the methyl radical loss process.

• 대한화학회지
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• 제10권3호
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• pp.119-128
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• 1966

The glass electrode was empirically calibrated in methanol-and 2-propanol-water mixed solvents, by means of which the pH-meter reading could be converted to stoichiometric hydrogen ion concentration. The thermodynamic dissociation constants of hydrogen cupferrate in methanol-and 2-propanol-water solution were potentiometrically determined with the changes in composition of organic solvents at 0.01 and 0.05 of the ionic strength and 25$^{\circ}C$. The empirical formula of the constants with mole fraction (n) of the organic solvent are as follow: methanol-water solution $pK_a$= 2.24n + 4.29 at ${\mu}$ = 0.01 n = 0.0476∼0.642 $pK_a$ = 2.35n + 4.38 at ${\mu}$ = 0.05 n= 0.0446~0.642 2-propanol-water solution $pK_a$= 5.50n + 4.48 at ${\mu}$ = 0.05 n = 0.0253~0.259 The relationships between $pK_a$ of acetic acid, propionic acid and HCup and dielectric constant of some mixed solvents were discussed. It would be considered that the factors effecting $pK_a$ value of weak acid in mixed-solvent are not only dielectric constants but acid-base character and solvation effect of the solvent, etc.

• 대한화학회지
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• 제19권1호
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• pp.11-15
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• 1975

Carbonyl 탄소원자의 반응성에 대한 연구의 일환으로 N,N-dimehtylcarbamoyl chloride와 N,N-diethylcarbamoyl chloride의 할로겐 교환반응을 아세톤 용매속에서 방사성 할라이드 이온을 사용하여 두 온도에서 속도론적으로 연구하였다. 그 결과를 alkylchloroformate의 경우와 비교하면, 친핵성의 순서는 비슷한 경향을 나타내나, 반응속도는 가용매분해나 alkylchloroformate의 경우보다 느리다. 활성화 피라미터 ${\Delta}H^*$나${\Delta}S^*$는$Cl^{\rightarrow}Br^{\rightarrow}I^-$는순서로 감소한다. 이 결과를 용매화 효과, bond-breaking, bond-formation 및 electronic requirment로 설명하였다.

• 대한화학회지
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• 제37권3호
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• pp.279-286
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• 1993

물-메탄올 혼합용매에서 KCl의 용매화에 미치는 압력의 효과를 알기 위하여 여러 가지 압력하에서 물-메탄올 혼합 용매의 밀도와 점성도 및 이 혼합용매하에서 KCl의 무한희석시 당량 전도도를 측정하여 r-함수를 구하였다. 25$^{\circ}C$, 1기압에서 KCl의 r-함수는 물에서는 0.613이나 메탄올의 양이 증가함에 따라 감소하다가 다시 증가하였으며 고압하에서도 대기압에서와 비슷한 변화의 경향을 보였다. 일정 압력하에서는 메탄올의 양이 증가함에 따라 r-함수가 감소하다가 다시 증가하였으나, 일정 용매조성에서 압력이 증가하면 r-함수는 감소하였다.

• 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.

• 한국자기공명학회논문지
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• 제22권4호
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• pp.139-143
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• 2018

Short antimicrobial peptide, A4W, have been studied by molecular dynamics (MD) simulation in an explicit dodecylphosphocholine (DPC) micelle. Peptide was aligned with DPC micelle and transferred new peptide-micelle coordinates within the same solvent box using specific micelle topology parameters. After initial energy minimization and equilibration, the conformation and orientation of the peptide were analyzed from trajectories obtained from the RMD (restrained molecular dynamics) or the subsequent free MD. Also, the information of solvation in the backbone and the side chain of the peptide, hydrogen bonding, and the properties of the dynamics were obtained. The results showed that the backbone residues of peptide are either solvated using water or in other case, they relate to hydrogen bonding. These properties could be a critical factor against the insertion mode of interaction. Most of the peptide-micelle interactions come from the hydrophobic interaction between the side chains of peptide and the structural interior of micelle system. The interaction of peptide-micelle, electrostatic potential and hydrogen bonding, between the terminal residues of peptide and the headgroups in micelle were observed. These interactions could be effect on the structure and flexibility of the peptide terminus.

• 공업화학
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• 제16권5호
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• pp.684-688
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• 2005

산도가 각기 다른 양성자산(HF, HCI, HBr, HI, $H_2SO_4$)의 수용액내에서 아닐린을 중합하였다. 이때 산도(pH)와 상대이온(counter ion)의 반응성에 따른 반응속도에 관하여 조사하였다. 반응속도에 대한 양성자산의 영향을 조사하기 위하여, open-circuit potential을 측정하였다. 그 결과 HF 수용액내에서 중합속도가 가장 느리게 나타났고, HI 수용액내에서는 중합반응이 진행되지 않았으며, 이러한 결과들을 산도(pH)와 산화력과의 관계로 설명하였다. 양성자산의 종류에 따라 dimer들의 생성비율도 각기 다르게 나타났으며, 이러한 결과들을 상대이온(음이온)의 친핵성도 (nucleophilicity), 용매화효과 및 이동도의 영향으로 설명하였다.