• Bulletin of the Korean Chemical Society
• /
• v.32 no.4
• /
• pp.1268-1272
• /
• 2011

The specific rates of solvolysis of phenyl fluorothionoformate (PhOCSF, 1) have been determined in 22 pure and binary solvents at $10.0^{\circ}C$. The extended Grunwald-Winstein equation has been applied to the specific rates of solvolysis of 1 over the full range of solvents. The sensitivities (l = $1.32{\pm}0.13$ and m = $0.39{\pm}0.08$) toward the changes in solvent nucleophilicity and solvent ionizing power, and the $k_F/k_{Cl}$ values are similar to those previously observed for solvolyses of acyl haloformate esters, consistent with the addition step of an additionelimination pathway being rate-determining. The large negative values for the entropies of activation are consistent with the bimolecular nature of the proposed rate-determining step. The results are compared with those reported earlier for phenyl chloroformate and chlorothionoformate esters and mechanistic conclusions are drawn.

• Transactions of the Korean hydrogen and new energy society
• /
• v.19 no.1
• /
• pp.56-63
• /
• 2008

In this study, thermochemical degradation of hemicellulose by Acetone-Solvolysis, the effects of reaction temperature, conversion yield, degradation properties and degradation products were investigated. Experiments were performed in a tube reactor by varying reaction temperature from $200{\circ}C$ to $400{\circ}C$ at 40 min of reaction time. The liquid products from pyrolysis-liquefaction of hemicellulose contained various kinds of ketones. ketones, as 4-methyl-3-penten-2-one, 3-methylene-2-pentanone, 22,6-dimethyl-2, 5-heptadien-4-one, 4-methyl-2-pentanone, 5-methyl-2-hexanone, 3,5,5-trimethyl-2-cyclohexen-1-one, and bezenes. as 1,4-dimethylbenzene, 1-methyl-2-(1-methylethyl)-benzene, 1,4-dimethyl-2-(2-methylpropyl)benzene, 4-secbutyl-ethyl benzene, could be used as high-octane-value fuels and fuel additives. Combustion heating value of liquid products from thermochemical conversion processes of hemicellulose was in the range of $6,680{\sim}7,170cal/g$. After 40min of reaction at $400{\circ}C$ in Acetone-Solvolysis of hemicellulose, the energy yield and mass yield was as high as 72.2% and 41.2g oil/100g raw material, respectively.

• Journal of the Korean Chemical Society
• /
• v.7 no.4
• /
• pp.264-270
• /
• 1963

The general equation for the substituent effect test, which was derived in the previous paper, has been extended to correlate thermodynamic parameters of solvolysis reaction by modifying the potential energy term to represent the effect of changes in solvent composition. The linear fits of the new equation, $\Delta{\Delta}H^\neq=a'Y+b\Delta{\Delta}S^\neq$, were tested with 35 examples from literature and average correlation coefficient of 0.977 was obtained. Examination of results showed that the equation is generally applicable to solvolysis reaction and helps elucidate some the difficulties experienced with the Grunwald-Winsteln equation. It has been stressed that the linear enthalpy-entropy effect exists only between the external enthalpy and entropy of activation, and therefore strictly it is the linear external enthalpy-entropy effect.

• Bulletin of the Korean Chemical Society
• /
• v.32 no.7
• /
• pp.2413-2417
• /
• 2011

The specific rates of solvolysis of 1- naphthyl chloroformate (1-NaphOCOCl, 1) and 2-naphthyl chloroformate (2-NaphOCOCl, 2) have been determined in a wide range of solvents at 2.0 and 10.0$^{\circ}C$. These give a satisfactory correlation over the full range of solvents when the extended (two-term) Grunwald-Winstein equation is applied. The sensitivities (l and m-values) to changes in solvent nucleophilicity ($N_T$) and solvent ionizing power ($Y_{Cl}$) are similar to those reported previously for solvolysis of phenyl chloroformate, which has been suggested to proceed through an addition-elimination mechanism with the addition step being rate determining. For four representative solvents, studies were made at several temperatures and activation parameters determined. These observations were also compared with those previously reported for phenyl chloroformates and naphthoyl chlorides.

• Bulletin of the Korean Chemical Society
• /
• v.19 no.3
• /
• pp.349-353
• /
• 1998

Solvolysis rates of substituted 2-aryl-1,1-dimethylethyl bromides (1) were determined in a variety of solvents such as aqueous mixtures of ethanol, acetone, 2,2,2-trifluoroethanol, and also mixtures of ethanol and TFE at 25 ℃, 35 ℃, and 45 ℃. The solvent effects were analyzed in terms of Winstein-Grunwald equation. The solvent effects of 1-4-MeO failed to give a single linear correlation against either Y or YCl (YBr), but exhibited a wide split pattern which could not be related to the solvent nucleophilicity. On the other hand 1-4-CH3 and 1-H gave a fairly good linearity. In the case of 1-4-MeO, a fairly good linearity was observed against YΔ defined from the solvolysis of 4-methoxyneophyl tosylate. It is assumed that resonance interaction between reaction site and aryl-π-system operates to give charge delocalization regardless of the different solvolysis mechanisms. The Hammett-Brown treatment of the solvolytic rate constant of compounds 1 was obtained non-linear two separated lines of - 1.06 to - 1.46, suggesting of mechanistic changeover from kc-ks to kΔ on going from electron-withdrawing to electron-donating substituents as a basis of 4-CH3 group.

• Journal of the Korean Chemical Society
• /
• v.30 no.1
• /
• pp.3-8
• /
• 1986

The investigation of the effect of solvent structure on the first-order solvolysis of cis-$[Co(en)_2ClNO_2]^+$ion has been extended to water + co-solvent mixtures where the co-solvents are glycerol, ethylene glycol, isopropyl alcohol and t-butyl alcohol. Rates of solvolysis have been evaluated by spectrophotometric method at temperature 25∼30$^{\circ}$C. The polarity of solvent has influence on the variation of rate constant. The non-linear plot of the rate constant in log scale versus $\frac{D-1}{2D+1}$ implies that change in solvent structure with composition plays an important role in determining the variation of rate constant. The linearity of the plot of the rate constant in log scale versus the Grundwald-Winstein Y factor confirms that the solvolysis is an Id-type process with considerable extension of the metal chloride bond in the transition state. In the Kivinen equation the slope of the plot of log k versus $log(H_2O)$ suggests that the solvolysis is also an Id-type process. The application of free energy cycle shows that the effect of solvent structure is greater in the transition state than in the initial state.

• Journal of the Korean Chemical Society
• /
• v.24 no.5
• /
• pp.342-346
• /
• 1980

Rates and activation parameters have been determined for the solvolysis of N, N-dimethylsulfamoyl chloride in aqueous binaries of MeOH, EtOH, $(Me)_2CO$ and MeCN. Various solvent effect correlation showed that the solvolysis proceeded via the dissociative $S_n2$ mechanism.

• Journal of the Korean Chemical Society
• /
• v.15 no.4
• /
• pp.205-209
• /
• 1971

The thermodynamic parameters for the solvolysis of the p-chlorobenzyl chloride taking place in the various aqueous mixtures were determined. From the application of these data to the formula ${\delta}_M{\Delta}H^{\neq}=a'Y+b{\delta}_M{\Delta}S^{\neq}$ the following conclusion was obtained: That the substrate constant a' differs in different aqueous solvent was found, and using each a' value the solvolysis mechanism of p-chlorobenzyl chloride in each aqueous mixture can be determined.

• Journal of the Korean Chemical Society
• /
• v.10 no.1
• /
• pp.11-14
• /
• 1966

The thermodynamic parameters for the solvolysis of the p-nitrobenzyl chloride which take place in the ethanol-water mixture media were determined. From the application of this data to the formula ${\delta}_M{\Delta}H^{\neq} = a'Y + b{\delta}_M{\Delta}S^{\leq}$ the following conclusion was obtained. The substrate constant a' for this reaction was not varied in the media which contain more than 50% alcohol and less than 50% alcohol. From this, it is clear that the mechanism of this reaction is the same both in the water-rich solvent and in the alcohol-rich solvent.

• Journal of the Korean Chemical Society
• /
• v.17 no.4
• /
• pp.235-239
• /
• 1973

Kinetic studies of benzoyl chlorides solvolysis have been carried out in acetone-water mixtures. Results show that bimolecular process predominates in the low water content region but SN1 process becomes increasingly important in the high water content solvent composition.