• Journal of Electrochemical Science and Technology
• /
• v.13 no.2
• /
• pp.237-253
• /
• 2022

The methyl 2-(1,3-dithietan -2- ylidene)-3-oxobutanoate (MDYO) and 2-(1,3-dithietan-2-ylidene) cyclohexane -1,3-dione (DYCD) were synthesized and tested at various concentrations as corrosion inhibitors for 316L stainless steel in 1 M HCl using weight loss, electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP), surface analysis techniques (SEM / EDX and Raman spectroscopy) and Functional Density Theory (DFT) was also used to calculate quantum parameters. The obtained results indicated that the inhibition efficiency of MDYO and DYCD increases with their concentration, and the highest value of corrosion inhibition efficiency was determined in the range of concentrations investigated (0.01 × 10^-3 - 10^-3 M). Polarization curves (Tafel extrapolation) showed that both compounds act as mixed-type inhibitors in 1M HCl solutions. Electrochemical impedance spectra (Nyquist plots) are characterized by a capacitive loop observed at high frequencies, and another small inductive loop near low frequencies. The thermodynamic data of adsorption of the two compounds on the stainless steel surface and the activation energies were determined and then discussed. Analysis of experimental results shows that MDYO and DYCD inhibitors adsorb to the metal surface according to the Langmuir model and the mechanism of adsorption of both inhibitors involves physisorption. SEM-EDX results confirm the existence of an inhibitor protective film on the stainless steel surface. The results derived from theoretical calculations supported the experimental observation.

• Journal of the Korean Society for Marine Environment & Energy
• /
• v.13 no.1
• /
• pp.18-29
• /
• 2010

Offshore subsurface storage of $CO_2$ is regarded as one of the most promising options to response severe climate change. Marine geological storage of $CO_2$ is to capture $CO_2$ from major point sources, to transport to the storage sites and to store $CO_2$ into the offshore subsurface geological structure such as the depleted gas reservoir and deep sea saline aquifer. Since 2005, we have developed relevant technologies for marine geological storage of $CO_2$. Those technologies include possible storage site surveys and basic designs for $CO_2$ transport and storage processes. To design a reliable $CO_2$ marine geological storage system, we devised a hypothetical scenario and used a numerical simulation tool to study its detailed processes. The process of transport $CO_2$ from the onshore capture sites to the offshore storage sites can be simulated with a thermodynamic equation of state. Before going to main calculation of process design, we compared and analyzed the relevant equation of states. To evaluate the predictive accuracies of the examined equation of states, we compare the results of numerical calculations with experimental reference data. Up to now, process design for this $CO_2$ marine geological storage has been carried out mainly on pure $CO_2$. Unfortunately the captured $CO_2$ mixture contains many impurities such as $N_2$, $O_2$, Ar, $H_{2}O$, $SO_{\chi}$, $H_{2}S$. A small amount of impurities can change the thermodynamic properties and then significantly affect the compression, purification and transport processes. This paper analyzes the major design parameters that are useful for constructing onshore and offshore $CO_2$ transport systems. On the basis of a parametric study of the hypothetical scenario, we suggest relevant variation ranges for the design parameters, particularly the flow rate, diameter, temperature, and pressure.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
• /
• v.14 no.3
• /
• pp.223-234
• /
• 2016

This study aimed to the adsorption-removal of high- radioactive iodide (I) contained in the initially generated high-radioactive seawater waste (HSW), with the use of AgX (Ag-impregnated X zeolite). Adsorption of I by AgX (hereafter denoted as AgX-I adsorption) was increased by increasing the Ag-impregnated concentration in AgX, and its concentration was suitable at about 30 wt%. Because of AgCl precipitation by chloride ions contained in seawater waste, the leaching yields of Ag from AgX (Ag-impregnated concentration : about 30~35 wt%) was less than those in distilled water (< 1 mg/L). AgX-I adsorption was above 99% in the initial iodide concentration ($C_i$) of 0.01~10 mg/L at m/V (ratio of weight of adsorbent to solution volume)=2.5 g/L. This shows that efficient removal of I is possible. AgX-I adsorption was found to be more effective in distilled water than in seawater waste, and the influence of solution temperature was insignificant. Ag-I adsorption was better described by a Freundlich isotherm rather than a Langmuir isotherm. AgX-I adsorption kinetics can be expressed by a pseudo-second order rate equation. The adsorption rate constants ($k_2$) decreased by increasing $C_i$, and conversely increased by increasing the ratio of m/V and the solution temperature. This time, the activation energy of AgX-I adsorption was about 6.3 kJ/mol. This suggests that AgX-I adsorption is dominated by physical adsorption with weaker bonds. The evaluation of thermodynamic parameters (a negative Gibbs free energy and a positive Enthalpy) indicates that AgX-I adsorption is a spontaneous reaction (forward reaction), and an endothermic reaction indicating that higher temperatures are favored.

• Korean Chemical Engineering Research
• /
• v.55 no.5
• /
• pp.723-730
• /
• 2017

The batch experiments by response surface methodology (RSM) have been applied to investigate the influences of operating parameters such as temperature, initial concentration, contact time and adsorbent dosage on 2,4-dichlorophenol (2,4-DCP) adsorption with an activated carbon prepared from waste citrus peel (WCAC). Regression equation formulated for the 2,4-DCP adsorption was represented as a function of response variables. Adequacy of the model was tested by the correlation between experimental and predicted values of the response. A fairly high value of $R^2$ (0.9921) indicated that most of the data variation was explained by the regression model. The significance of independent variables and their interactions were tested by the analysis of variance (ANOVA) and t-test statistics. These results showed that the model used to fit response variables was significant and adequate to represent the relationship between the response and the independent variables. The kinetics and isotherm experiment data can be well described with the pseudo-second order model and the Langmuir isotherm model, respectively. The maximum adsorption capacity of 2,4-DCP on WCAC calculated from the Langmuir isotherm model was 345.49 mg/g. The rate controlling mechanism study revealed that film diffusion and intraparticle diffusion were simultaneously occurring during the adsorption process. The thermodynamic parameters indicated that the adsorption reaction of 2,4-DCP on WCAC was an endothermic and spontaneous process.

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

• Journal of the Korea Academia-Industrial cooperation Society
• /
• v.21 no.7
• /
• pp.667-674
• /
• 2020

The adsorption of reactive orange 16 (RO 16) dye by activated carbon was investigated using the amount of adsorbent, pH, initial concentration, contact time and temperature as adsorption variables. The investigated process parameters were separation coefficient, rate constant, rate controlling step, activation energy, enthalpy, entropy, and free energy. The adsorption of RO 16 was the highest at pH 3 due to the electrostatic attraction between the cations (H⁺) on the surface of the activated carbon and the sulfonate ions and hydroxy ions possessed by RO 16. Isotherm data were fitted into Langmuir, Freundlich and Temkin isotherm models by applying the evaluated separation factor of Langmuir (RL=0.459~0.491) and Freundlich (1/n=0.398~0.441). Therefore, the adsorption operation of RO 16 by activated carbon was confirmed as an appropriate removal method. Temkin's adsorption energy indicated that this adsorption process was physical adsorption. The adsorption kinetics studies showed that the adsorption of RO 16 follows the pseudo-second-order kinetic model and that the rate controlling step in the adsorption process was the intraparticle diffusion step. The positive enthalpy change indicated an endothermic process. The negative Gibbs free energy change decreased in the order of -3.16 <-11.60 <-14.01 kJ/mol as the temperature increased. Therefore, it was shown that the spontaneity of the adsorption process of RO 16 increases with increasing temperature.

• Journal of the Korean Electrochemical Society
• /
• v.10 no.3
• /
• pp.219-228
• /
• 2007

The phase-shift method and correlation constants, i.e., the electrochemical impedance spectroscopy (EIS) techniques for studying linear relationships between the behaviors (${\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and those (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}{\theta}{\geq}0$), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) of H for the cathodic $H_2$ evolution reaction (HER) at noble and transition-metal/aqueous solution interfaces. At the Pt/0.1 MKOH aqueous solution interface, the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=5.6{\times}10^{-10}\;mol^{-1}\;at\;0{\leq}{\theta}<0.81$, $K=5.6{\times}10^{-9}{\exp}(-4.6{\theta})\;mol^{-1}\;at\;0.2<{\theta}<0.8$, and $K=5.6{\times}10^{-10}{\exp}(-12{\theta})\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$, interaction parameters (g = 4.6 for the Temkin and g = 12 for the Frumkin adsorption isotherm), rates of change of the standard free energy ($r=11.4\;kJ\;mol^{-1}$ for g=4.6 and $r=29.8\;kJ\;mol^{-1}$ for g=12), and standard free energies (${\Delta}G_{ads}^0=52.8\;kJ\;mol^{-1}\;at\;0{\leq}{\theta}<0.81,\;49.4<{\Delta}G_{\theta}^0<56.2\;kJ\;mol^{-1}\;at\;0.2<{\theta}<0.8$ and $80.1<{\Delta}_{\theta}^0{\leq}82.5\;kJ\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$) of OH for the anodic $O_2$ evolution reaction (OER) are also determined using the phase-shift method and correlation constants. The adsorption of OH transits from the Langmuir to the Frumkin adsorption isotherm (${\theta}\;vs.E$), and vice versa, depending on the electrode potential (E) or the fractional surface coverage (${\theta}$). At the intermediate values of ${\theta}$, i.e., $0.2<{\theta}<0.8$, the Temkin adsorption isotherm (${\theta}\;vs.\;E$) correlating with the Langmuir or the Frumkin adsorption isotherm (${\theta}\;vs.\;E$), and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are accurate and reliable techniques to determine the adsorption isotherms and related electrode kinetic and thermodynamic parameters. They are useful and effective ways to study the adsorptions of intermediates (H, OH) for the sequential reactions (HER, OER) at the interfaces.

• Applied Chemistry for Engineering
• /
• v.23 no.5
• /
• pp.450-455
• /
• 2012

The paper includes the utlization of an activated carbon as a potential adsorbent to remove a hazardous fluorescein dye from an aqueous solution. Batch adsorption experiments were carried out for the removal of fluorescein dyes using a granular activated carbon as an adsorbent. The effects of various parameters such as pH, amount of adsorbent, contact time, initial concentration and temperature of the adsoprtion system were investigated. The experimental results revealed that activated carbon exhibit high efficiencies to remove fluorescein dyes from the aqueous solution. The equilibrium process can be well described by Freundlich isotherm in the temperature range from 298 K to 318 K. From adsorption kinetic experiments, the adsorption process followed a pseudo second order kinetic model, and the adsorption rate constant ($k_2$) decreased with increasing the initial concentration of fluorescein. The free energy of adsorption ${\Delta}G^0$), enthalpy ${\Delta}H^0$), and entropy (${\Delta}S^0$) change were calculated to predict the nature adsorption. The estimated values for ${\Delta}G^0$ were -17.11~-20.50 kJ/mol over an activated carbon at 250 mg/L, indicated toward a spontaneous process. The positve value for ${\Delta}H^0$, 33.2 kJ/mol, indicates that the adsorption of fluorescein dyes on an activated carbon is an endothermic process.

• Journal of the Korean Chemical Society
• /
• v.38 no.8
• /
• pp.539-546
• /
• 1994

The critical micelle concentration(CMC) and the counterion binding $constant(\beta)$ at the CMC of cetyltrimethylammonium bromide(CTAB) in a series of aqueous solutions containing medium chain-length n-alcohols(Propanol, Butanol, Pentanol and Hexanol) have been determined from the concentration dependence of electrical conductance at serveral temperature from $17^{\circ}C\;to\;41^{\circ}C.$ Thermodynamic parameters $({\Delta}G^o_m,\;{\Delta}H^o_m,\;{\Delta}S^o_m,\;and\;{\Delta}C_p)$ associated with micelle formation of CTAB have been also estimated from the temperature dependence of CMC and $\beta$ values, and the significance of these parameters and their relation to the theory of micelle formation have been considered. The results show that an enthalpy-entropy compensation effect is usually observed for the micellization of CTAB. The effects of n-alcohols on the micellar properties (CMC and $\beta$) of CTAB solutions have been also investigated. The addition of n-alcohol to the CTAB solution in a small quantity decreases the CMC value and the counterion binding constant $(\beta)$ at the CMC, but the addition of n-alcohol in an excessive quantity increases the CMC values on the conterary. These results have been explained in terms of the effect of the micelle-solubilized alcohol on the micellar surface charge density.

• Journal of the Korean Chemical Society
• /
• v.55 no.4
• /
• pp.612-619
• /
• 2011

Lanthanide(III) complexes of 1,2-diphenyl-4-butyl-3,5-pyrazolidinedione(phenylbutazone, PB) have been synthesized and characterized by elemental analyses, molar conductance measurements, IR, UV-Vis. and NMR spectra. The spectral data reveal that the PB acts as a bidentate and mono-ionic ligand coordinating through both the carbonyl oxygens of the pyrazolidinedione ring. The molar conductance data suggest that the complexes are non-electrolytes. The thermal behaviour of the complexes was studied by TG and DTG in air atmosphere and the results provide information about dehydration, thermal stability and thermal decomposition. The final products are found to be the corresponding metal oxides. The thermodynamic parameters and kinetic parameters were evaluated for the dehydration and decomposition stages. The negative entropy values of the decomposition stages indicate that the activated complexes have a more ordered structure than the reactants and that the reactions are slower than normal. Based on these studies, the complexes have been formulated as $[Ln(PB)_3]{\cdot}5H_2O$(Ln=La and Ce) and $[Ln(PB)_3(H_2O)_2]{\cdot}2H_2O$(Ln=Pr, Nd and Sm).