• Corrosion Science and Technology
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• v.5 no.5
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• pp.160-167
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• 2006

S-Acetyl Isothiourea Acetate (S-AITA) was synthesized in the laboratory and this influence on the inhibition of corrosion of mild steel in 1.11 N hydrochloric and 1.12 N sulphuric acids was investigated by weight loss and potentiostatic polarization techniques at 303K, 353K and 403K. These results were confirmed by the impedance technique. The inhibition efficiency increased with increase in concentration of inhibitor and decreased with rise in temperature from 303K to 403K. The maximum inhibition efficiency of S-AITA was found to be 99.95% (0.5% of S-AITA) at 303K in sulphuric acid. The adsorption of this compound on the mild steel surface from the acids has been found to obey Temkin's adsorption isotherm. The potentiostatic polarization results revealed that S-AITA was a mixed type inhibitor. Some thermodynamic parameters i.e., activation energy (Ea), free energy of adsorption (${\Delta}G_{ads}$), enthalpy of adsorption (${\Delta}H$) and entropy of adsorption (${\Delta}S$) were also calculated from weight loss data.

• Bulletin of the Korean Chemical Society
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• v.23 no.5
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• pp.715-720
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• 2002

Kinetic studies of the reaction of Z-aryl cyclobutanecarboxylates with X-pyridines in acetonitrile at $55.0^{\circ}C$ have been carried out. The reaction proceeds by a stepwise mechanism in which the rate-determining step is the breakdown of the zwitterion ic tetrahedral intermediate, T $\pm$ . These mechanistic conclusions are drawn based on (i) the large magnitude of ${\rho}X$ and $\rhoZ$, (ⅱ) the positive sign of ${\rho}XZ$ and the larger magnitude of $\rhoXZ$ than normal SN2 processes, (ⅲ) a small positive enthalpy of activation, ${\Delta}H{\neq}$, and a large negative, ${\Delta}S{\neq}$, and lastly (iv) adherence to the reactivity-selectivity principle (RSP) in all cases.

• Proceeding of EDISON Challenge
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• 2015.03a
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• pp.117-123
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• 2015

본 연구에서는 DFT를 이용하여 Nucleophilicity와 Basicity의 연관성에 대한 계산화학적 분석을 수행하였다. Basicity는 선정된 모델 분자의 protonation 반응에서 생성물과 반응물의 enthalpy 변화량인 양성자 친화도(Proton affinity, PA) 값을 구하여 분석하였다. 계산한 결과는 실험을 통해 얻은 PA 결과와 경향성이 거의 일치함을 확인하였다. Nucleophilicity는 모델 분자들과 $CH_3Br$ (electrophile)의 $SN_2$반응에서 gibbs free energy of activation(${\Delta}G^{\ddag}$) 값으로 그 경향성을 분석하였다. 또한 용매의 종류를 다르게 하여 용매에 따른 ${\Delta}G^{\ddag}$ 값의 경향성도 확인하였다. 각 용매에 따라 구한 ${\Delta}G^{\ddag}$와 PA의 상관관계를 비교하였으나, 큰 연관성은 보이지 않았다. 이에 ${\Delta}G^{\ddag}$와 PA의 상관관계를 보여줄 수 있는 parameter를 찾기 위하여 각 모델 분자의 Electronegativity와 Polarizability를 계산하여 연관성을 비교해보았다. Polarizability를 적용했을 때 Nucleophilicity와 Basicity사이의 연관성을 나타낼 수 없었던 반면, Electronegativity를 적용하여 Basicity와 Nucleophilicity의 연관성 보일 수 있음을 이론적으로 규명하였다.

• Analytical Science and Technology
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• v.14 no.4
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• pp.349-355
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• 2001

A series of micro- and mesoporous activated carbons were prepared from phenolic resin using a metal treated chemical activation methodology. $N_2$-adsorption data were used to characterize the surface properties of the produced activated carbons. Results of the surface properties and pore distribution analysis showed that phenolic resin can be successfully converted to micro- and mesoporous activated carbons with specific surface areas higher than $962.3m^2/g$. Activated carbons with porous structure were produced by controlling the amount of metal chlorides($CdCl_2$, $CuCl_2$). Pore evolvement was shown to be most effected by the incremental addition of metal chloride. From the thermodynamic DSC data, enthalpy formations(${\Delta}H$) of first endothermic reaction were increase with the incremental addition of metal chloride.

• Clean Technology
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• v.17 no.2
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• pp.97-102
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• 2011

The adsorption characteristics of amatanth dye by granular activated carbon were experimently investigated in the batch adsorption. Kinetic studies of adsorption of amaranth dye were carried out at 298, 308 and 318 K, using aqueous solutions with 100, 200 and 300 mg/L initial concentration of amatanth. It was established that the adsorption equilibrium of amaranth dye on granular activated carbon was successfully fitted by Langmuir isotherm equation at 298 K. The pseudo first order and pseudo second order models were used to evaluate the kinetic data and the pseudo second order kinetic model was the best with good correlation. Values of the rate constant ($k_2$) have been calculated as 0.1076, 0.0531, and 0.0309 g/mg h at 100, 200 and 300 mg/L initial concentration of amatanth, respectively. Thermodynamic parameter such as activation energy, standard enthalpy, standard entropy and standard free energy were evaluated. The estimated values for standard free energy were -5.08 - -8.10 kJ/mol over activated carbon at 200 mg/L, indicated toward a spontaneous process. The positive value for enthalpy, 38.89 kJ/mol indicates that adsorption interaction of amatanth dye on activated carbon is an endothermic process.

• Bulletin of the Korean Chemical Society
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• v.31 no.7
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• pp.1988-1992
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• 2010

4-Amino-1,2,4-triazole copper complex (4-ATzCu) was synthesized, and its thermal behaviors, nonisothermal decomposition reaction kinetics were studied by DSC and TG-DTG techniques. The thermal decomposition reaction kinetic equation was obtained as: $d\alpha$ / dt =$10^{22.01}$ (1-$\alpha$)[-ln(1-$\alpha$)]$^{1/3}$ exp($-2.75\times10^4$ /T). The standard mole specific heat capacity of the complex was determined and the standard molar heat capacity is 305.66 $J{\cdot}mol^{-1}{\cdot}K^{-1}$ at 298.15 K. The entropy of activation $({\Delta}S^{\neq})$, enthalpy of activation $({\Delta}H^{\neq})$, and Gibbs free energy of activation $({\Delta}G^{\neq})$ are calculated as 171.88 $J{\cdot}mol^{-1}{\cdot}K^{-1}$ 225.81 $kJ{\cdot}mol^{-1}$ and 141.18 $kJ{\cdot}mol^{-1}$, and the adiabatic time-to-explosion of the complex was obtained as 389.20 s.

• Journal of the Korean Chemical Society
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• v.20 no.6
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• pp.479-485
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• 1976

The rate of the bromine-exchange reaction between gallium bromide and n-butyl bromide in 1,2,4-trichlorobenzene and in nitrobenzene was measured at 19, 25 and 40$^{\circ}C$., using n-butyl bromide labelled with Br-82. The results indicated that the exchange reaction was second order with respect to gallium bromide and first order with respect to n-butyl bromide. The third-order rate constant determined at $19^{\circ}C.$ is 1.15{\times}10^{-4} l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$ in 1,2,4-trichlorobenzene and $4.21{\times}10^{-4} l^2·$$mole^{-2}{\cdot}sec^{-1}$ in nitrobenzene. The activation energy, the enthalpy of activation and the entropy of activation for the exchange reaction were also determined.

• Journal of the Korean Chemical Society
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• v.27 no.3
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• pp.201-207
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• 1983

The rate constants for solvated electrons with benzene in the binary mixture (tetrahydrofuran-water) were measured at a various temperatures$(-18{\circ}C{\sim}+51{\circ}C)$ by photolysis. From Arrhenius plots of rate constants it was observed that the activation energies were decreased with increasing tetrahydrofuran(THF) content. Decreasing the viscosity of solvent mixtures by adding water, the rate constants were also decreased. It indicates that the reaction of solvated electrons are not controlled by diffusion. The change of activation enthalpy in kcal $M^{-1}$ and the rate constants in$ M^{-1}sec^{-1}$ were 4.90 and $8.80{\times}10^8$ for 30M% of THF, 2.80 and $5.14{\times}10^8$ for 49M% of THF, and -0.30 and %1.43{\times}10^8$ for 75M% of THF, respectively. The slope of the linear plot of activation enthalpies against activation entropies was $244{\circ}K$, which supports the reaction parameter is the change of activation entropy in the range of the experimental temperature. From the solvent effect on the activation energy, it was found that the step of the reaction, ${e_s}^-+B{\rightleftharpoons}B^-$ shifted to the exothermic reaction with increasing THF content.

• Resources Recycling
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• v.11 no.6
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• pp.38-46
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• 2002

Fundamental investigations were conducted far the recovery process of waste organic solvent by fractional distillation in the aspects of equilibrium and kinetics. Mixture of toluene and xylene, which were both being used in the largest amount as industrial organic solvent, was taken as the artificial waste organic solvent and their distillation behaviors were studied. The purity of recovered solvent was investigated by Cir Chromatography and shown to be in the range of 94～98%. Based upon equilibrium calculations, the changes in the Gibbs free energy, standard enthalpy, and standard entropy for distillation reaction have been estimated. The standard enthalpy changes for toluene and xylene were shown to be 44.833 and 47.044 kJ $mol^{-1}$ respectively, which were similar to their molar heats of evaporation. The activation energies of distillation fur toluene and xylene obtained from kinetic studies were 3.281 and 2.699 kJ $mol^{-1}$ and they were about one tenths of the standard enthalpy changes of distillation reaction. The highness of the purity of recovered organic solvents suggested the possibility that the recovered waste organic sol-vent could partly replace the original solvent.

• Applied Chemistry for Engineering
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• v.24 no.2
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• pp.184-189
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• 2013

In the present study, batch experiments were carried out for the utilizatioin of activated carbon as a potential adsorbent to remove a hazardous malachite green from an aqueous solution. The effects of various parameters such as temperature, contact time, initial concentration on the adsorption system were investigated. On the basis of adsorption data Langmuir and Freundlich adsorption isotherm model were also confirmed. The equilibrium process was described well by Langmuir isotherm model. From determined separation factor, the activated carbon could be employed as an effective treatment for removal of malachite green. From kinetic experiments, the adsorption process followed the pseudo second order model, and the adsorption rate constant ($k_2$) decreased with increasing both the initial concentration of malachite green and the adsoprtion temperature. Thermodynamic parameters like that activation energy, change of free energy, enthalpy, and entropy were also calculated to predict the adsorption nature. The activation energy calculated from Arrhenius equation indicated that the adsortpion of malachite green on the zeolite was physical process. The negative Gibbs free energy change ($\Delta$G = -3.68~-7.76 kJ/mol) and the positive enthalpy change ($\Delta$H = +26.34 kJ/mol) indicated the spontaneous and endothermic nature of the adsorption in the temperature range of 298~318 K.