• Transactions of the Korean hydrogen and new energy society
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• v.20 no.1
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• pp.55-63
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• 2009

In this study, thermochemical degradation by acetone solvolysis reaction of siberian spruce wood was investigated for a temperature range of $200{\sim}400^{\circ}C$. The liquid products by acetone solvolysis from siberian spruce wood produced various kinds of aliphatics, cyclic compounds and aromatics included phenols etc. Combustion heating value of liquid products by acetone solvolysis conversion processes was in the range of $8,010{\sim}8,180cal/g$. The energy yield in acetone solvolysis of siberian spruce wood was as high as 74.2% after 40min of reaction at $400^{\circ}C$. The liquid products from the thermochemical conversion of siberian spruce wood could be used as high-octane-value fuels and fuel additives.

• Journal of the Korean Wood Science and Technology
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• v.25 no.4
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• pp.45-50
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• 1997

This research was studied for dissolving pulp preparation as the raw material of viscose rayon from woody biomass by solvolysis pretreatment. In the change of pulp characteristic after solvolysis pretreatment, the following results were obtained. In the case of solvolysis pretreatment, we have obtained pulp that high purity cellulose, and degree of polymerization was inclined to decrease less than 440 on the phosphoric acid as catalyst. Comparing phosphoric acid and formic acid as catalyst in the solvolysis pretreatment, using on formic acid catalyst is superior to phosphoric acid catalyst for making dissolving pulp.

• Transactions of the Korean hydrogen and new energy society
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• v.16 no.2
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• pp.159-169
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• 2005

Cellulose, consisted of 45 wt% in wood, is usable as fuels and heavy oil additives if depolymerized to monomer unit, because the chemical structures are similar to high octane materials found in gasoline. In this study, thermochemical degradation by solvolysis reaction of cellulose such as the effect of reaction temperature, reaction time and type of solvent on conversion yield and degradation products were investigated. It was found that the effectiveness of the solvent on the sovolysis reaction was as follows; acetone>n-butanol>tetralin. When acetone was used as a solvent, the highest cellulose conversion was observed to be 91.8% at 500$^{\circ}C$, 40min. Combustion heating value of liquid products from thermochemical conversion processes was in the range of 7,330${\sim}$7,410cal/g. The energy yield and mass yield in acetone-solvolysis of cellulose was as high as 66.8% and 37.0 g oil/100g raw material after 40min of reaction at 400$^{\circ}C$. Various aliphatic and aromatic compounds were detected in the cellulose solvolysis products. The major components of the solvolysis products, that could be used as fuel, were mesityl oxide, mesitylene, isophorone.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2263-2270
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• 2014

Solvolysis rate constants of 2-phenylethyl-(2-$PhCH_2CH_2OCOCl$, 1) and 2,2-diphenylethyl chloroformate (2,2-$Ph_2CHCH_2OCOCl$, 2), together with the previously studied solvolyses of ${\alpha}$- and ${\beta}$-substituted chloroformate ester derivatives, are reported in pure and binary solvents at $40.0^{\circ}C$. The linear free energy relationship (LFER) and sensitivities (l and m) to changes in solvent nucleophilicity ($N_T$) and solvent ionizing power ($Y_{Cl}$) of the solvolytic reactions are analyzed using the Grunwald-Winstein equation. The kinetic solvent isotope effects (KSIEs) in methanol and activation parameter values in various solvents are investigated for 1 and 2. These results support well the bimolecular pathway with same aspects. Furthermore, the small negative values of the entropies of activation of solvolysis of 1 and 2 in the highly ionizing aqueous fluoroalcohols are consistent with the ionization character of the rate-determining step, and the KSIE values of 1.78 and 2.10 in methanol-d indicate that one molecule of solvent acts as a nucleophile and the other acts as a general-base catalyst. It is found that the ${\beta}$-substituents in alkyl chloroformate are not the important factor to decide the solvolysis reaction pathway.

• Transactions of the Korean hydrogen and new energy society
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• v.18 no.1
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• pp.85-94
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• 2007

Rice straw, produced as an agricultural by-product, is usable biomass as fuels if depolymerized to monomer unit, because the chemical structure are similar to high octane materials found in gasoline. In this study, parameters of thermochemical degradation by solvolysis reaction of rice straw such as the effect of reaction temperature, reaction time and type of solvent on conversion yield and degradation products were investigated. It was found that the effectiveness of the solvent on the solvolysis reaction was as follows; acetone>cresol>butanol. When acetone was used as a solvent, the highest rice straw conversion was observed to be 91.5% at $500^{\circ}C$, 40 min. Combustion heating value of liquid products from thermochemical conversion processes was in the range of 7,380 cal/g. The energy yield and mass yield in acetone-solvolysis of rice straw was as high as 69.0% and 38.2 g-oil/100g-raw material after 40 min of reaction at $350^{\circ}C$. Various aliphatic and aromatic compounds were detected in the rice straw solvolysis products. The major components of the solvolysis products, that could be used as fuel, were 4-methyl-2-pentanone, 3,5,5-trimethyl-2-cyclopentan-1-one as ketones.

• Bulletin of the Korean Chemical Society
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• v.17 no.11
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• pp.1056-1061
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• 1996

Solvolysis rates of 1-(4-methoxyphenyl)-l-phenyl-2,2,2-trifiuoroethyl chloride (1) and 1-(4-methoxyphenyl)-1-phenylethyl chloride (2) were measured in a variety of aqueous binary solvents, and the solvent effect was treated with the Grunwald-Winstein equation. The solvent effect on the solvolysis of 1 failed to give a single linear correlations using the ordinary Y or YCl, but exhibited the wide split pattern which could not be related to the solvent nucleophilicity. The improved correlations with YBnCl and extended dual-parameter treatment, log (k/k0)=mYCl+hI (mΔYΔ), were observed for the solvolysis of 1. These results suggest that the incipient cationic charge in the solvolysis of 1 is delocalized strongly into the aryl-rings in the transition state. While the solvent effect on the solvolysis of 2 is better correlated with Y or YCl than YBnCl but the linearity is not satisfactory. The correlation is comparably improved by the use of the extended Grunwald-Winstein equation, log (k/k0)=0.81YCl+0.26NOTs (R=0.994, SD=±0.12), indicating the cationic charge of reaction center of 2 was localized mostly in the transition state.

• Journal of the Korean Chemical Society
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• v.15 no.5
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• pp.219-222
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• 1971

The kinetics of the solvolysis of benzyl and p-or m-substituted benzyl bromides in various alcohols have been determined by an electric conductivity method. From these reactions, a curved Hammett plot is obtained and a mechanism is proposed to account for the nonlinear behavior observed. In addition, effects of solvent polarity on the activation parameters for the solvolysis of benzyl bromides are discussed.

• Bulletin of the Korean Chemical Society
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• v.3 no.1
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• pp.30-33
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• 1982

Photochemical and thermal solvolysis of 2,3,4-picolyl chlorides (2,3,4-PC) were studied in amine solvents and the results were correlated with the electronic structures calculated by PPP-SCF-MO CI method. Activation parameters show that the thermal solvolysis of PC is $S_N2$ type rcaction. The rates of thermal reaction in pyridine or t-butylamine solvent decrease in the order of 2-PC > 3-PC > 4-PC. These results are consistent with the predictions based on the electron densities of picolyl chlorides. In photosolvolysis, the same products as those of thermal reactions were obtained. The results indicate that photochemical solvolysis undergoes through heterolytic cleavage. Relative quantum yields of photosolvolysis of 2,3,4-picolyl chlorides in t-butylamine solvent were determined to be 0.73, 1, and 0.50 respectively. These results are in good agreement with the electron densities of the excited triplet state of picolyl chlorides.

• Journal of the Korean Chemical Society
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• v.65 no.5
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• pp.309-312
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• 2021

The solvolysis of (1s)-(+)-menthyl chloroformate (1) were studied kinetically in 28 pure and various mixed solvents. The analysis using the extended Grunwald-Winstein equation in the solvolysis of 1 obtained the l value of 2.46 ± 0.18, the m value of 0.91 ± 0.07, and the correlation coefficient of 0.950. The solvolysis of 1 might proceed via an associative S_N2 mechanism enhancing bond making than bond breaking in the transition state (TS). The value of l/m is 2.7 within the ranges of value found in associative S_N2 reaction. This interpretation is further supported by a relatively large solvent kinetic isotope effect (SKIE, 2.16).

• Bulletin of the Korean Chemical Society
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• v.17 no.3
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• pp.228-234
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• 1996

The rates of solvolysis of 1-(4-methoxyphenyl)-1-aryl-2,2,2-trifluoroethyl chlorides[I] in a variety of solvents were measured by an electroconductometric method. LArSR relationships (Yukawa-Tsuno eq.)were found to give a linear plot, log(k/ko)=-1.84[σo+0.918(σ+-σo)], in 80% aqueous ethanol. Small |ρ| and r values in comparison with 1-aryl-1-(trifluoromethyl)ethyl tosylate(ρ=-6.09, r=1.59) suggested that the carbocationic charge in the transition state was dispersed by a strong p-π donor, p-methoxy group. Linear mY plots with m 0.90 for all of the substituents in aqueous acetone and m=0.60-0.82 for those of aqueous ethanol indicate that this solvolysis proceeds via an SN1 mechanism with nucleophilic solvent assistance. Thiourea effects and isokinetic temperatures for the rate of solvolysis also can prove the above mechanism.