• Bulletin of the Korean Chemical Society
• /
• v.17 no.9
• /
• pp.802-807
• /
• 1996

Second-order rate constants have been measured spectrophotometrically for the reactions of aryl benzoates (X-C6H4CO2C6H4-Y) with EtO-, Z-C6H4O- and Z-C6H4C(Me)=NO- in absolute ethanol at 25.0 ℃. All the reactions have been performed in the presence of excess 18-crown-6 ether in order to eliminate the catalytic effect shown by alkali metal ion. A good Hammett correlation has been obtained with a large ρ- value (-1.96) when σ- (Z) constant was used for the reaction of p-nitrophenyl benzoate (PNPB) with Z-C6H4O-. Surprisingly, the one for the reaction of PNPB with Z-C6H4C(Me)=NO- gives a small but definitely positive ρ- value (＋0.09). However, for reactions of C6H5CO2C6H4-Y with EtO-, correlation of log k with σ- (Y) constant gives very poor Hammett correlation. A significantly improved linearity has been obtained when σ0 (Y) constant was used, indicating that the leaving group departure is little advanced at the TS of the RDS. For reactions of X-C6H4CO2C6H4-4-NO2 with EtO-, C6H5O- and C6H5C(Me)=NO-, correlations of log k with σ (X) constants for all the three nucleophile systems give good linearity with large positive ρ values, e.g. 2.95, 2.81 and 3.06 for EtO-, C6H5O- and C6H5C(Me)=NO-, respectively. The large ρ values clearly suggest that the present reaction proceeds via a stepwise mechanism in which the formation of the addition intermediate is the RDS.

• Bulletin of the Korean Chemical Society
• /
• v.14 no.5
• /
• pp.603-610
• /
• 1993

The crystal structure of dehydrated $Ag_{5.6}K_{6.4}-A$, zeolite A ion-exchanged with $K^+\;and\;Ag^+$ as indicated and dehydrated at 360$^{\circ}$C, has been determined by single-crystal X-ray diffraction techniques. Also determined were the structures of the products of the reactions of this zeolite with 0.1 Torr of Cs vapor at 250$^{\circ}$C for 48 h and 72 h, and with 0.1 Torr of Rb vapor at 250$^{\circ}$C for 24 h. The structures were solved and refined in the cubic space group Pm3m at 21(l)$^{\circ}$C (a= 12.255(l) ${\AA}$ , 12.367(l) ${\AA}$, 12.350(l) ${\AA}$, and 12.263(l) ${\AA}$, respectively). Dehydrated $Ag_{5.6}K_{6.4}$-A was refined to the final error indices $R_1= 0.044\;and\;R_2=0.037$ with 202 reflections for which I>3${\sigma}$(I). The crystal structures of the reaction products were refined to $R_1=0.087\;and\;R_2= 0.089$ with 157 reflections, $R_1=0.080\;and\;R_2= 0.087$ with 161 reflections, and $R_1= 0.071\;and\;R_2=0.061$ with 88 reflections, respectively. In the structure of $Ag_{5.6}K_{6.4}-A,\;K^+$ ions block all 8-oxygen rings, and one reduced Ag atom is found per sodalite cavity. Also, ca. 4.6 $Ag^+ ions\;and\;3.4 K^+ ions$ are found at 6-ring sites in the large cavity. The crystal structures of the reaction products show that all $K^+$ and $Ag^+$ ions have been reduced, and that all K^+$ atoms have left the zeolite. Cs or Rb species are found at three different crystallographic sites: 3.0 $Cs^+\;or\;3.0Rb^+$ ions per unit cell occupy 8-ring centers, ca. 8.0 $Cs^+ ions\;or\;5.7 Rb^+$ ions, are found on threefold axes opposite 6-rings deep in the large cavity, and ca. 2.5 $Cs^+\;or\;2.3 Rb^+ ions are found on threefold axes in the sodalite unit. Also, 1 $Rb^+$ ion lies opposite a 4-ring. Silver atoms, corresponding to 75% or 40% occupancy of hexasilver clusters stabilized by coordination to $Cs^+\;or\;Rb^+$ ions, are found at the centers of the large cavities. In the crystal structures of dehydrated Ag_{5.6}K_{6.4}-A$ reacted with Cs vapor, excess Cs atoms are absorbed and these form (locally) cationic clusters such as $(Cs_4)3^+\;and\;(Cs_6)4^+$.

• Journal of the Korean GEO-environmental Society
• /
• v.8 no.2
• /
• pp.5-9
• /
• 2007

This study carried out to investigate the removal capacity of heavy metals such as Cu (II), Zn (II) and Cd (II) dissolved in aqueous solution in the soils collected from Hyeon-Dong (HD), San-seong (SS), Keum-chon (KC) and Keum-Hac (KH) located in the upper Banbyun stream. The pH of all the soils was weak alkali such as 8.8 9.2. According to the analysis of chemical composition of the soils, the amount of $SiO_2$, $AlO_2$ and CaO were similar in all tested soils. However, the amount of $K_2O$, $FeO_3$ and MgO were different from each soil. The XRD measurement with these soils showed that quartz and feldspar were presented in all tested soils, and the distribution of kaoline, illite, montmorillonite, vermiculite and calcite were different from each soil. The results of the removal capacity of heavy metals indicated that all the soils had more than 98% of the removal efficiency of Cu (II), Zn (II) and Cd (II), and among the heavy metals, Cu (II) was removed the most effectively. These results suggested that the soils collected from the upper Banbyun stream have the high removal capacity of heavy metals, and these soils could be used for the banking a river around the abandoned mine area, containing the higher concentrations of heavy metals than the usual stream.

• Membrane Journal
• /
• v.28 no.3
• /
• pp.157-168
• /
• 2018

Potassium tannate (TA-K), which is prepared by base treatment of the bio-renewable tannic acid (TA), was evaluated for its potential application as a draw solute for water purification by forward osmosis. The forward osmosis and recovery properties of TA-K were systematically investigated. In the application of forward osmosis through the active layer facing feed solution (AL-FS) method, the water flux of TA-K draw solution was significantly higher than that of the TA draw solution, while that of the latter was not identified. At a low concentration of 100 mM, the osmotic pressure (1,135 mOsmol/kg) of the TA-K draw solution was approximately 6.5 times that (173 mOsmol/kg) of the NaCl draw solution. Furthermore, the water flux and specific salt flux (6.14 LMH, 1.26 g/L) of the TA-K draw solution at 100 mM were approximately 2.5 and 0.5 times those of the NaCl draw solution (2.46 LMH, 2.63 g/L) at the same concentration, respectively. For reuse, TA-K was precipitated by using a metal ion and recovered through membrane filtration. This study demonstrates the applicability of a phytochemical material as a draw solute for forward osmosis.

• Economic and Environmental Geology
• /
• v.35 no.4
• /
• pp.325-337
• /
• 2002

We examined the contamination of stream water and stream sediments by heavy metal elements with respect to distance from the abandoned Backun Au-Ag-Cu mine. High contents of heavy metals (Pb, Zn, Cu, Cd, Mn, and Fe) and aluminum in the waters connected with mining and associated deposits (dumps, tailings) reduce water quality. In the mining area, Ca and SO$_4$ are predominant cation and anion. The mining water is Ca-SO$_4$ type and is enriched in heavy metals resulted from the weathering of sulfide minerals. This mine drainage water is weakly acid or neutral (pH; 6.5-7.1) because of neutralizing effect by other alkali and alkaline earth elements. The effluent from the mine adit is also weakly acid or neutral, and contains elevated concentrations of most elements due to reactions with ore and gangue minerals in the deposit. The concentration of ions in the Backun mining water is high in the mine adit drainage water and steeply decreased award to down stream. Buffering process can be reasonably considered as a partial natural control of pollution, since the ion concentration becomes lower and the pH value becomes neutralized. In order to evaluate mobility and bioavailability of metals, sequential extraction was used for stream sediments into five operationally defined groups: exchangeable, bound to carbonates, bound to FeMn oxide, bound to organic matter, and residual. The residual fraction was the most abundant pool for Cu(2l-92%), Zn(28-89%) and Pb(23-94%). Almost sediments are low concentrated with Cd(2.7-52.8 mg/kg) than any other elements. But Cd dominate with non stable fraction (68-97%). Upper stream sediments are contaminated with Pb, and down area sediments are enriched with Zn. It is indicate high mobility of Zn and Cd.