• Journal of the Korean Chemical Society
• /
• v.18 no.3
• /
• pp.157-170
• /
• 1974

The effects of ionic strength on the polynucleation reaction of tungstate ions and the protonized reaction of polytungstate ions have been investigated in the range of ionic strength from 1 M to 4 M KCl.The hexatungstate ions and the protonized forms of hexatungstate ions are formed in the tungstate solutions whose ionic strengths are 1 M to 4 M KCl. The equilibrium constants for the formation of hexatungstate ions and the protonized forms of hexatungstate ions are calculated in the range of ionic strength from 1 M to 4M KCl. The enthalpy changes for the formation of hexatungstate ions and the protonized forms of hexatungstate ions are as follows; $7H^++{6WO_4}^{2-}={HW_6O_{21}}^{5-}+3H_2O\;\;{\Delta}H^{\circ}=-62.4{\pm}0.6$$H^++{HW_6O_{21}}^{5-}={H_2W_6O_{21}}^{4-}\;\;{\Delta}H+_1^{\circ}=-4.12{\pm}0.10$$H^++{H_2W_6O_{21}}^{4-}={ H_3W_6O_{21}}^{3-}\;\;{\Delta}H_2^{\circ}=-4.36{\pm}0.30$ The free energy and entropy changes for the above reactions have been also calculated. A linear relation is formed between $log k_{6,7}$ and ionic strength, and $log k_1\;or\;log k_2\;vs{\cdot}{\mu}.$ $log k_{6,7}\;=\;D{\mu}+I,\;\;where\;D\;=\;1.66{\pm}0.02$$log k_1\;=\;D_1{\mu}+I_1,\;\;where\;D_1\;=\;-8.065{\pm}0.001$$log k_2\;=\;D_2{\mu}+I_2,\;\;where\;D_2\;=\;-0.376{\pm}0.006$

• Applied Chemistry for Engineering
• /
• v.5 no.3
• /
• pp.406-412
• /
• 1994

The ion-exchange properties of $Ca^{2+}$ and $Mg^{2+}$ ions have been studied in ${\delta}-Na_2Si_2O_5$ synthesized from water glass. Results show that optimum temperature for synthesis of ${\delta}-Na_2Si_2O_5$ was $725^{\circ}C$. Ion-exchange isotherms for $Ca^{2+}$ and $Mg^{2+}$ exchange for $Na^+$ in the synthetic ${\delta}-Na_2Si_2O_5$ show that the ion-exchange capacity of magnesium is better than that of calcium, and the ion-exchange of magnesium is less sensitive for temperature than that of calcium. When initial pH of solution is increased between 2 and 6, the ion-exchange capacities of magnesium and calcium decrease a little. However, they are almost constant above pH 6 because of alkali buffer effect of ${\delta}-Na_2Si_2O_5$. In the thermodynamic studies, it was found that Gibbs free energies of reaction of calcium ion-exchange are larger than those of magnesium ion-exchange with inverse order of selectivity. The standard enthalpy and entropy of reaction of calcium ion-exchange are larger than those of magnesium ion-exchange.

• The Korean Journal of Food And Nutrition
• /
• v.29 no.3
• /
• pp.371-381
• /
• 2016

The present study investigated the effects of processing parameters such as time (10, 20, 30, 40 min), pressure (25, 50, 75, 100 MPa), and the salinity of brine (0~10%(w/v)) on jacopever (Sebastes schlegeli Hilgendorf) in order to establish optimization of the three factors using a high hydrostatic pressure (HHP) machine. To do so, it analyzed the quality characteristics of volatile basic nitrogen (VBN), trimethylamine (TMA), total bacterial counts, dynamic viscoelasticities, and differential scanning calorimetry (DSC) properties. First, when the time increased to 40 mins, by 10 min intervals, the total bacterial counts in HHP groups under $25^{\circ}C$, 100 MPa, and 4%(w/v) brine were significantly decreased except for the first 10 min in comparison to the control group. In regards to DSC properties, the onset temperature ($T_O$) of the first endothermal curve was significantly reduced. Second, when the pressure level increased up to 100 MPa by 25 MPa increments, the total bacterial counts in the HHP samples significantly decreased for 20 min at 50 MPa or higher. As the pressure increased, G', G" and the slope of tan ${\delta}$ decreased (except for 50 MPa). Third, in regards to the salinities of brine, when the HHP processing was treated at 100 MPa, $25^{\circ}C$ for 20 min, the total bacterial counts of all the HHP groups significantly decreased in comparison to those of the control group. A significant difference was found in the enthalpy of the second endothermic curve in the 6~10%(w/v) (except 7%(w/v)) HHP groups. Therefore, the salinity of the immersion water under the HHP condition was appropriate when it was lower than 6%(w/v). The present study demonstrated that the optimum parameter condition according to/under the condition of the microbial inhibition and economic effects using an HHP would be the reaction time for 20 min, reaction pressure at 100 MPa, and the salinity of 4%(w/v) brine.

• Journal of the Korean Chemical Society
• /
• v.18 no.5
• /
• pp.320-328
• /
• 1974

It is unable to derive the standard emf ($E^{\circ}$) of the cell at high pressure from the conventional method. However, when the concept of the complete equilibrium constant($K{\circ})$) is available to the conventional Nernst equation, it is possible to get the standard emf of the cell at high pressure(complete Nernst equation). Moreover, the other thermodynamic properties, such as the net change of solvation number(k), the compressibility of solvent(${\beta}$), ionization constant(K), the standard free energy change(${\Delta}G^{\circ}$), the standard enthalpy change(${\Delta}H^{\circ}$) and the standard entropy change (${\Delta}S^{\circ}$) of the cell reaction at equilibrium state have been also obtained. In this experiment, the emf of the cell; 12.5 % Cd(Hg)│$CdSO_4(3.105{\times}10^{-3}M),\;Hg_2SO_4│Hg$ have bee measured at temperature from 20 to $35^{\circ}C$ and at pressures from 1 to 2500 atms. The emf of the cell increased with increasing pressure at constant temperature, and did with increasing temperature at constant pressure. The net change of solvation number(k) of the cell reaction was 41.96 at $25^{\circ}C$, and kept constant value with pressure, while, K and ${\Delta}S^{\circ}$ increased with pressure, but whereas ${\Delta}G^{\circ}$ and ${\Delta}H^{\circ}$ decreased. Since the standard emf of the cell at high pressure can be calculated from the complete Nernst equation, the theory of chemical equilibrium could be developed with at high pressure as well as at the atmosphere.

• Clean Technology
• /
• v.25 no.1
• /
• pp.56-62
• /
• 2019

The equilibrium, kinetic and thermodynamic parameters of adsorption of murexide by granular activated carbon were investigated. The experiment was carried out by batch experiment with the variables of the amount of the adsorbent, the initial concentration of the dye, the contact time and the temperature. The isothermal adsorption equilibrium was best applied to the Freundlich equation in the range of 293 ~ 313 K. From the separation factor (${\beta}$) of Freundlich equation, it was found that adsorption of murexide by granular activated carbon could be the appropriate treatment method. The adsorption energy (E) obtained from the Dubinin- Radushkevich equation shows that the adsorption process is a physical adsorption process. From the kinetic analysis of the adsorption process, pseudo second order model is more consistent than pseudo first order model. It was found that the adsorption process proceeded to a spontaneous process and an endothermic process through Gibbs free energy change ($-0.1096{\sim}-10.5348kJ\;mol^{-1}$) and enthalpy change ($+151.29kJ\;mol^{-1}$). In addition, since the Gibbs free energy change decreased with increasing temperature, adsorption reaction of murexide by granular activated carbon increased spontaneously with increasing temperature. The entropy change ($147.62J\;mol^{-1}\;K^{-1}$) represented the increasing of randomness at the solid-solution interface during the adsorption reaction of murexide by activated carbon.

• Korean Chemical Engineering Research
• /
• v.59 no.4
• /
• pp.565-573
• /
• 2021

Isotherms, kinetics and thermodynamic properties for adsorption of Brilliant Green(BG), Quinoline Yellow(QY) dyes by activated carbon were carried out using variables such as dose of adsorbent, pH, initial concentration, contact time, temperature and competitive. BG showed the highest adsorption rate of 92.4% at pH 11, and QY was adsorbed at 90.9% at pH 3. BG was in good agreement with the Freundlich isothermal model, and QY was well matched with Langmuir model. The separation coefficients of isotherm model indicated that these dyes could be effectively treated by activated carbon. Estimated adsorption energy by Temkin isotherm model indicated that the adsorption of BG and QY by activated carbon is a physical adsorption. The kinetic experimental results showed that the pseudo second order model had a better fit than the pseudo first order model with a smaller in the equilibrium adsorption amount. It was confirmed that surface diffusion was a rate controlling step by the intraparticle diffusion model. The activation energy and enthalpy change of the adsorption process indicated that the adsorption process was a relatively easy endothermic reaction. The entropy change indicated that the disorder of the adsorption system increased as the adsorption of BG and QY dyes to activated carbon proceeded. Gibbs free energy was found that the adsorption reaction became more spontaneous with increasing temperature. As a result of competitive adsorption of the mixed solution, it was found that QY was disturbed by BG and the adsorption reduced.

• Clean Technology
• /
• v.27 no.2
• /
• pp.182-189
• /
• 2021

The adsorption of disperse yellow 3 (DY 3) on granular activated carbon (GAC) was investigated for isothermal adsorption and kinetic and thermodynamic parameters by experimenting with initial concentration, contact time, temperature, and pH of the dye as adsorption parameters. In the pH change experiment, the adsorption percent of DY 3 on activated carbon was highest in the acidic region, pH 3 due to electrostatic attraction between the surface of the activated carbon with positive charge and the anion (OH^-) of DY 3. The adsorption equilibrium data of DY 3 fit the Langmuir isothermal adsorption equation best, and it was found that activated carbon can effectively remove DY 3 from the calculated separation factor (R_L). The heat of adsorption-related constant (B) from the Temkin equation did not exceed 20 J mol^-1, indicating that it is a physical adsorption process. The pseudo second order kinetic model fits well within 10.72% of the error percent in the kinetic experiments. The plots for Weber and Morris intraparticle diffusion model were divided into two straight lines. The intraparticle diffusion rate was slow because the slope of the stage 2 (intraparticle diffusion) was smaller than that of stage 1 (boundary layer diffusion). Therefore, it was confirmed that the intraparticle diffusion was rate controlling step. The free energy change of the DY 3 adsorption by activated carbon showed negative values at 298 ~ 318 K. As the temperature increased, the spontaneity increased. The enthalpy change of the adsorption reaction of DY 3 by activated carbon was 0.65 kJ mol^-1, which was an endothermic reaction, and the entropy change was 2.14 J mol^-1 K^-1.

• Applied Chemistry for Engineering
• /
• v.32 no.3
• /
• pp.283-289
• /
• 2021

Adsorption characteristics of carbol fuchsin (CF) dye by coal-based activated carbon (CAC) were investigated using pH, initial concentration, temperature and contact time as adsorption variables. CF dissociates in water to have a cation, NH₂⁺, which is bonded to the negatively charged surface of the activated carbon in the basic region by electrostatic attraction. Under the optimum condition of pH 11, 96.6% of the initial concentration was adsorbed. Isothermal adsorption behavior was analyzed using Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models. Langmuir's equation was the best fit for the experimental results. Therefore, the adsorption mechanism was expected to be adsorbed as a monolayer on the surface of activated carbon with a uniform energy distribution. From the evaluated Langmuir's dimensionless separation coefficients (R_L = 0.503~0.672), it was found that CF can be effectively treated by activated carbon. The adsorption energies determined by Temkin and Dubinin-Radushkevich models were E = 15.31~7.12 J/mol and B = 0.223~0.365 kJ/mol, respectively. Therefore, the adsorption process was physical (E < 20 J/mol, B < 8 kJ/mol). The experimental result of adsorption kinetics fit better the pseudo second order model. In the adsorption reaction of CF dye to CAC, the negative free energy change increased as the temperature increased. It was found that the spontaneity also increased with increasing temperature. The positive enthalpy change (40.09 kJ/mol) indicated an endothermic reaction.

• Resources Recycling
• /
• v.23 no.2
• /
• pp.17-25
• /
• 2014

The thermal effect on the compositional change of the $SO_2$ absorption process product was investigated compared with the composition of raw material when dolomite is employed in place of lime in the scrubbing process based on thermodynamic estimation. It was considered that the equilibrium reactions which directly related with the formation of $CaSO_4$ and $MgSO_4$, the absorption process products, are those between $Ca^{2+}$ and $Ca(OH)_2$, $Mg^{2+}$ and $Mg(OH)_2$, and the secondary dissociation reaction of $H_2SO_4$. It was thought to be necessary to examine the enthalpy change for the formation reactions of $CaSO_4$ and $MgSO_4$ along with the thermal feature of the relative reactions to figure out the influence of temperature on the compositional change of absorption process products. The stable regions for $Ca(OH)_2$ and $Mg(OH)_2$ in Pourbaix diagram were found to be increased as temperature rises and the equilibrium reaction between $Ca^{2+}$ and $Ca(OH)_2$ was investigated to be more strongly influence by temperature change compared with the equilibrium reaction between $Mg^{2+}$ and $Mg(OH)_2$. The amounts of $CaSO_4$ and $MgSO_4$ were anticipated to be decreased with temperature considering the thermal characteristics for the equilibrium reactions regarding calcium, magnesium, and $H_2SO_4$. It was understood that the formation ratio between $CaSO_4$ and $MgSO_4$ is greater than the composition ratio between calcium and magnesium contained in dolomite at specific temperature and the decrease of the formation ratio of $CaSO_4$ and $MgSO_4$ with temperature was estimated to be diminished as the content of calcium in dolomite is increased. In addition, the extent of the change in the compositional ratio between absorption process products was examined to be reduced compared with the composition of raw material as the calcium content in dolomite is raised.

• Journal of the Korean Chemical Society
• /
• v.17 no.3
• /
• pp.145-153
• /
• 1973

The temperature effects on the equilibria between polymolybdatd anions in 1M sodium perchlorate solution has been investigated in the temperature range of 20~50$^{\circ}$C. The polymolybdate anions formed are heptamolybdate ($Mo_7O_{24}^{6-}$) ions and the protonized forms of heptamolybdate ions ($H_LMo_7O_{24}^{(6-L)-}$). The equilibrium constants for the formation of heptamolybdate ions calculated by Sillen's method are as follow;$8H^{+}+7MoO_4^{2-}=Mo_7O_{24}^{6-}+4H_2O$, $k_{7.8}=2.77{\times}10^{53}:20^{\circ}C= 9.29{\times}10^{51}:40^{\circ}C$,$k_{7.8}= 4.22{\times}10^{52}:30^{\circ}C = 9.29{\times}10^{51}:50^{\circ}C$ The enthalpy change for calculated for the above reaction is 31.51 kcal/mole. A method of calculation of the equilibrium constants for the formation of protonized heptamolybdate ions from heptamolybdate ions and hydrogen ions has been derived. The equilibrium constants calculated for the formation of protonized heptamolybdate ions are as follow; $ LH^++ Mo_7O_{24}^{-6} = H_LMo_7O_{24}^{(6-L)-} : L = 1\;or\;2$, $k_1 = 2.31{\times}10^4=2.53{\times}10^4=2.76{\times}10^4= 3.10{\times}10^4$, $k_2 = 6.19{\times}10^7\;20^{\circ}C = 7.80{\times}10^7\;30^{\circ}C = 1.22{\times}10^8\;40^{\circ}C = 2.03{\times}10^8\;50^{\circ}C$The enthalpy change for the following step reactions are as follow;$H^{+}+Mo_7O_{24}^{6-}= HMo_7O_{24}^{5-}\;{\Delta}H^{\circ}=1.90 kcal/mole$, $2H^{+}+Mo_7O_{24}^{6-}=H_2Mo_7O_{24}^{4-}\;{\Delta}H^{\circ}=7.50kcal/mole$