• Bulletin of the Korean Chemical Society
• /
• v.34 no.1
• /
• pp.49-53
• /
• 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
• /
• v.23 no.9
• /
• pp.1263-1307
• /
• 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- .

• Journal of the Korean Chemical Society
• /
• v.24 no.6
• /
• pp.444-451
• /
• 1980

In order to further elucidate the process of electron solvation in liquids, the medium effect, as the difference between the free energy of $H^+$ in aqueous and non-aqueous states (${\Delta}{\Delta}G_0$), of THF-water mixtures has been investigated. (${\Delta}{\Delta}G_0$) were determined by electromotive force masurements of the cell Pt$H_2Q$, Q, HCI, THF, $H_2O$|KC1 | $Hg_2Cl_2$|Hg(Pt), where $H_2Q$ and Q are hydroquinone and quinone respectively. The effect of dielectric constant on the difference of free energy and the absorption energy of solvated electrons have been studied. For the consideration of these effect the polymerization of water in THF has been studied. Near infrared spectrum of O-H stetching energy has been used to measure the extent of water aggregates. The expermental results indicate that at least in some composition of binary mixtures the electrons or other ions are solvated preferentially with one component of solvents.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.8
• /
• pp.1519-1524
• /
• 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.

• Journal of the Korean Chemical Society
• /
• v.10 no.3
• /
• pp.119-128
• /
• 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.

• Journal of the Korean Chemical Society
• /
• v.19 no.1
• /
• pp.11-15
• /
• 1975

Kinetic study of halogen exchange for N,N-dimethylcarbamoyl chloride and N,N-diethylcarbamoyl chloride in acetone by using radioisotopic halide ions has been carried out at two temperatures as a part of studying the reactivity of carbonyl carbon atom. The order of nucleophilicity showed a similar tendency as that for alkyl chloroformate, but reaction rate is much slower than that for solvolysis and alkyl chloroformate. The activation parameters,${\Delta}H^*$and${\Delta}S^*$ were found to decrease in sequence $Cl^{\rightarrow}Br^{\rightarrow}I^-$ for N,N-dialkylcarbamoyl chlorides. The results are interpreted in terms of solvation effect, degree of bond-breaking and bond-formation and electronic requirements.

• Journal of the Korean Chemical Society
• /
• v.37 no.3
• /
• pp.279-286
• /
• 1993

The effect of pressure on solvation of potassium chloride was studied by the density and viscosity measurements of water-methanol systems and the conductance measurements of KCl in this systems. These were used to calculate the r-function of KCl. It was found that the r-function of KCl which is 0.613 at 25$^{\circ}C$ and 1 bar in water was continuously decreased to the minimum point and enhanced with increasing the composition of methanol. At high pressure, the r-function of KCl was similar to that of normal pressure. But r-function decreased with increasing pressure at the specific component of methanol.

• Bulletin of the Korean Chemical Society
• /
• v.4 no.3
• /
• pp.115-119
• /
• 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.

• Journal of the Korean Magnetic Resonance Society
• /
• v.22 no.4
• /
• pp.139-143
• /
• 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.

• Applied Chemistry for Engineering
• /
• v.16 no.5
• /
• pp.684-688
• /
• 2005

Aniline was polymerized in various protonic acid (HF, HC1, HBr, HI, $H_2SO_4$) aqueous solutions with different acidity. During the reaction, the dimer formation and the reaction rate were examined as functions of acidity (pH) and the size of counter ions. Open-circuit potential measurements were carried out to investigate the effect of protonic acid on the reaction rate. The results showed that polymerization rate in HF aqueous solution was very slow and polymerization did not occur in HI aqueous solution. These results were explained in terms of acidity and power of oxidation. The ratio of formation of dimers varied with the kind of protonic acid, and the results were explained with the nucleophilicity, solvation effect, and mobility of counter ions.