• Applied Chemistry for Engineering
• /
• v.17 no.2
• /
• pp.125-131
• /
• 2006

Dimethyl ether (DME) is a new clean fuel as an environmentally-benign energy resource. DME can be manufactured from various energy sources including natural gas, coal, biomass and spent plastic. In addition to its environmentally friendly properties, DME has similar characteristics to those of LPG. Therefore, it is considered as an excellent substitute fuel for LPG, fuel cells, power plant, and especially diesel and is expected to be the alternative fuel by 2010. The experimental study of the direct synthesis of DME was investigated under various conditions over a temperature range of $220{\sim}280^{\circ}C$, syngas ratio 1.2~3.0. All experiments were carried out with a hybrid catalyst, composed of a methanol synthesis catalyst ($Cu/ZnO/Al_2O_3$) and a dehydration catalyst (${\gamma}-Al_2O_3$). The observed reaction rate follows qualitatively a Langmiur-Hinshellwood model as the reaction mechanism. Such a mechanism is considered with three reactions; methanol synthesis, methanol dehydration and water gas shift reaction. From a surface reaction with dissociative adsorption of hydrogen, methanol, and water, individual reaction rate was determined.

• Bulletin of the Korean Chemical Society
• /
• v.14 no.6
• /
• pp.669-673
• /
• 1993

The CO substitution reactions of the complex, $Cp(S-2,4-Me_2C_5H_5)CrCo$ with $PR_3(PR_3=PMePh_2,\;P(OCH_3)_3,\;PMe_2Ph)$ were investigated spectrophotometrically at various temperatures. From the reaction rates, it was suggested that the CO substitution reaction took place by first-order (dissociative) pathway. Activation parameters in decaline were ${\Delta}H^{\neq}\;=\;22.0\;kcal{\cdot}mol^{-1}$, ${\Delta}S^{\neq}=\;-3.8cal{\cdot}mol^{-1}{\cdot}K^{-1}$. Unusually low value of ${\Delta}S{\neq}$ suggests an ${\eta}^5-S{\to}{\eta}^5-U$ conversion of the pentadienyl ligand. This suggestion was confirmed by the Extended-Huckel molecular orbital (EHMO) calculations, which revealed that the total energy of $Cp(S-2,4-Me_2C_5H_5$)CrCO is about 0.42 kcal/mol more lower than that of $Cp(U-2,4-Me_2C_5H_5)CrCO$ and the energy of $[Cp(U-2,4-Me_2C_5H_5)Cr{\cdots}CO]^{\neq} $ transition state is about 2.43 kcal/mol lower than that of $[Cp(S-2,4-Me_2C_5H_5)Cr{\cdots}CO]^{\neq}$ transition state.

• Bulletin of the Korean Chemical Society
• /
• v.14 no.2
• /
• pp.207-211
• /
• 1993

The CO substitution reactions in the complex, $Cp(S-C_5H_7)CrCO$ with $PR_3(PR_3=PMePh_2,\;P(OCH_3)_3,\;PMe_2Ph)$ were investigated spectrophotometrically at various temperatures. From the reaction rates, it was suggested that the CO substitution reaction takes place by first-order (dissociative) pathway. Activation parameters in decaline are ${\Delta}H^{\neq}\;=\;24.58\;kcal\;{\cdot}\;mol^{-1},\;{\Delta}S^{\neq}\;=\;3.05 cal\;{\cdot}\;mol^{-1}{\cdot}K^{-1}$. Unusually low value of ${\Delta}S^{\neq}$ suggests an ${\eta}^5-S\;{\to}\;{\eta}^5-U$ conversion of the pentadienyl ligand. This was confirmed by the extended-Huckel molecular orbital (EHMO) calculations, which revealed that the total energy Of $Cp(S-C_5H_7)CrCO$ is about 6.84 kcal/mol more stable than that of $Cp(U-C_5H_7)CrCO$ and the energy of $[Cp(U-C_5H_7)CrCO^{\neq}$ transition state is about 4.25 kcal/mol lower than that of $[Cp(S-C_5H_7)Cr]^{\neq}$ transition state.

• Journal of the Korean Vacuum Society
• /
• v.6 no.S1
• /
• pp.59-65
• /
• 1997

Efficient Si(100) etching by thermal H atoms at low substrate temperatures has been achieved. Gas-phase etching product $SiH_4$(g) upon H atom bombardment resulting from direct abstraction of $SiH_3$(a) by impinging H atoms was detected with a quadrupole mass spectrometer over the substrate temperature range of 105-408 K Facile depletion of all surface silyl ($SiH_3$) groups the dissociative adsorption product of disilane ($Si_2H_6$) at 105K from Si(100)2$\times$1 by D atoms and continuous regeneration and removal of $SiD_3$(a) were all consumed. These results provide direct evidence for efficient silicon surface etching by thermal hydrogen bombardment at cryogenic temperatures as low as 105K We attribute the high etching efficiency to the formation and stability of $SiH_3$(a) on Si(100) at lowered surface temperatures allowing the $SiH_3$(a) abstraction reaction by additional H atom to produce $SiH_4$((g).

• Bulletin of the Korean Chemical Society
• /
• v.9 no.6
• /
• pp.388-393
• /
• 1988

The chemisorption of CO molecules on polycrystalline nickel surface has been studied by investigating the resulting chemisorbed species with the X-ray photoelectron spectroscopy at temperatures between 300K through 433K. It is found that the adsorbed CO molecules are dissociated by the simple C-O bond cleavage as well as by the disproportionation reaction at temperatures above 373K. The former type dissociation is more favored at low coverages and at elevated temperatures. The isotherms of CO chemisorption are obtained from the xps intensities of C 1s peaks, and then the activation energy of the dissociative adsorption is estimated as a function of the CO exposure. These activation energies are extrapolated to zero coverage to obtain the activation energy of chemisorption in which thermal C-O bond cleavage takes place. The value obtained is 38.1 kJ/mol.

• Bulletin of the Korean Chemical Society
• /
• v.4 no.5
• /
• pp.208-211
• /
• 1983

Kinetic studies of nucleophilic substitution reactions of para-substituted benzylchlorides with anilines were conducted in a range of MeOH-MeCN mixtures at $55.1^{\circ}C$. Hammett ${\rho}_C$, ${\rho}_N$ values and Bronsted ${\beta}$ values were determined, in other to examine the transition state variations caused by changes in nucleophiles, substituents and solvents properties (${\pi}^{\ast}$ and ${\alpha}$). Applications of potential energy surface (PES) and quantum mechanical (QM) models of transitheion state characterization lead us to conclude that the reaction proceeds via the dissociative $S_N2$ mechanism.

• Journal of the Korean Chemical Society
• /
• v.35 no.1
• /
• pp.64-69
• /
• 1991

Kinetics of the reaction of p-methylphenacyl arenesulfonates with pyridine in acetonitrile were investigated by an electric conductivity method at 1∼2000 bars and 35∼55$^{\circ}C$. The rates of these reactions were increased with raising pressures and temperatures. The activation enthalpy(${\Delta}H^{\neq}$), entropy(${\Delta}S^{\neq}$) and activation volume(${\Delta}V^{\neq}$) of the reaction were obtained with the rate constants. Activation volume and entropy were both negative valued, and activation enthalpy was positive. The acteivation parameters (${\Delta}V^{\neq}$ and ${\Delta}S^{\neq}$) were decreased with increasing pressure. From all of the above results, it was found that this reaction proceeds on the S$_N$2 in which C${\cdots}$O bond breaking is more advanced as pressure increases.

• Journal of the Korean Chemical Society
• /
• v.37 no.11
• /
• pp.951-960
• /
• 1993

$Hg^{2+}$-induced aquation trans-[Co(3,2,3-tet)$X_2]^+$(3,2,3-tet = 4,7-diazadecane-1,10-diamine, $X_2\;=\;Cl_2,\;(NO_2)Cl,\;Br_2,\;(NO_2)Br,\;(NO_3)_2)$ complexes was investigated in aqueous solution. The products and the reaction mechanism were confirmed by chromatography, UV/Vis. spectrum, and circular dichroism (CD) spectrum. From the results, $Hg^{2+}$-induced aquation of 3,2,3-tet system has been produced cis-${\beta}$ complex via trans complex. The kinetic studies on $Hg^{2+}$-induced aquation of trans-[Co(3,2,3-tet)$Cl_2]^+$ complex and trans-[Co(3,2,3-tet)$(NO_2)Cl]^+$ complex were also carried out to study the reaction mechanism. The results show that trans-[Co(3,2,3-tet)$Cl_2]^+$ complex undergoes the D(dissociative)-mechanism and trans-[Co(3,2,3-tet)$(NO_2)Cl]^+$ complex $I_d$(interchange dissociavite)-mechanism. In order to confirm steric course for the reaction mechanism, $Hg^{2+}$-induced aquation on trans-[Co(R,R-3,2,3-tet)$Cl_2]^+$ complex to which chiral R,R-3,2,3-tet was coordinated instead of the racemic(R,R:S,S) 3,2,3-tet was used has been examined by CD spectrum. From the results, the final complex was confirmed to be ${\Delta}-cis-{\beta}$-[Co(R,R-3,2,3-tet)$(OH_2)_2]^{3+}$ complex indicating the chirality was retained through whole process.

• Journal of the Korean Chemical Society
• /
• v.38 no.1
• /
• pp.41-49
• /
• 1994

Exchange reaction mechanisms of the Pb(II) ion for the complexes between Pb(II) ion and nitrogen oxygen donor macrocyclic ligands, such as 1,13-diaza-3,4 : $1011-dibenzo-59-dioxacyclohexa-decane(NtnOtnH_4)$, 1,15-diaza-3,4 : $1213-dibenzo-5811-trioxacycloheptadecane(NenOdienH_4)$, and 1,15-diaza-3,4 : $1213-dibenzo-5811-trioxacyclooctadecane(NtnOdienH_4)$, were studied by $^{207}Pb-NMR$ spectroscopy in N,N'-dimethylformamide(DMF) solutions. The associative-dissociative mechanism dominated in $NtnOtnH_4-Pb(II)$ and $NtnOdienH_4-Pb(II)$ system. For $NenOdienH_4-Pb(II)$ system, the bimolecular exchange mechanism prevailed below $-5^{\circ}C$, and both bimolecular exchange and associative-dissociative mechanism dominated above $+5^{\circ}C.$ The order of activation energies for dissociation was $NtnOdienH_4\;<\;NtnOtnH_4\;<\;NenOdienH_4$ which was reverse to the order of stabilities.

• Bulletin of the Korean Chemical Society
• /
• v.14 no.5
• /
• pp.549-554
• /
• 1993

The CO substitution reactions in the complex, $Cp^*(C_5H_7)$CrCO with $PR_3(PR_3=PMePh_2,\;P(OCH_3)_3,\;PMe_2Ph)$ were investigated spectrophotometrically at various temperatures. For the reaction rates, it was suggested that the CO substitution reaction took place by first-order (dissociative) pathway. Activation parameters in decaline are ${\Delta}H^{\neq}= 21.99{\pm}2.4$ kcal/mol, ${\Delta}S^{\neq}= 8.9{\pm}7.1$ cal/mol·k. Unusually low value of ${\Delta}S^{\neq}$, suggested an ${\eta}^5-S{\to}\;{\eta}^5$-U conversion of the pentadienyl ligand. At various temperature, the rates of reaction for the Cp(pdl)CrCO complexes increase in the order $Cp^*(C_5H_7)$-CrCO < Cp$(C_5H_7)$CrCO < Cp(2,4-$C_5H_{11}$)CrCO, which can be attributed to the usual steric acceration or electronic influence for the ligand substitution of metal complexes. This suggestion was confirmed by the extended-Huckel molecular orbital (EHMO) calculations, which revealed that the energy of $[Cp^*(U-C_5H_7)Cr]^{\neq}$ transition state is about 4.93 kcal/mol lower than that of [Cp(S-$C_5H_7)Cr]^{\neq}$ transition state, and the arrangement of the overlap populations between Cr and the carbon of CO is $Cp^*(C_5H_7)$CrCO > Cp($C_5H_7$)CrCO > Cp(2,4-$C_7H_{11}$)CrCO.