• Analytical Science and Technology
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• v.5 no.1
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• pp.41-49
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• 1992

An attempt was made to prepare two series of tetrakis eight-coordinate tungsten(IV) and cerium(IV) complexes containing the 5,7-dichloro-8-quinolinol(N:${\pi}$-acceptor atom, O:${\pi}$-donor atom) ligand. Tetrakis eight-coordinate tungsten(IV) complex of 2-mercaptopyrimidine(N:${\pi}$-acceptor atom, S:${\pi}$-donor atom) ligand have also been prepared. And the new series of mixed-ligand eight-coordinate tungsten(IV) complexes containing bidentate ligands 5,7-dichloro-8-quinolinol and 2-mercaptopyrimidine have been prepared, isolated by TLC and characterized. $W(dcq)_4$, $W(dcq)_3(mpd)_1$, $W(dcq)_2(mpd)_2$, $W(dcq)_1W(dcq)_3$ and $W(mpd)_4$ complexes of MLCT absorption band appeared to 710nm, 680nm, 625nm, 581nm, and 571nm(${\varepsilon}\;max={\sim}>{\times}10^4$) on low-energy respectively. The specific absorption wave length of $Ce(dcq)_4$ is appeared 520nm(${\varepsilon}\;max={\sim}>{\times}10^4$). The Chemical shift values by proton of coordinated position appeared to $W(dcq)_4$ [$H_2:8.9ppm$]; $W(dcq)_3(mpd)_1$ [$H_2:9.3$,$H_6:9.2ppm$]; $W(dcq)_2(mpd)_2$ [$H_2:9.7$,$H_6:8.95ppm$]; $W(dcq)_1(mpd)_3$ [$H_2:9.8$,$H_6:9.4ppm$]; $W(mpd)_4$ [$H_6:8.8ppm$]; $Ce(dcq)_4$ [$H_2:9.3ppm$] with $^1H$-NMR. The inertness of mixed-ligand eight coordinate tungsten(IV) complexes have been investigated by UV-Vis. spectroscopic method in dimethylsulfoxide at $90^{\circ}C$. The inertness of $W(dcq)_n(mpd)_{4-n}$ complexes showed the following order, $W(dcq)_3(mpd)_1;k_{obs.}=3.8{\times}10^{-6}$ > $W(mpd)_4;k_{obs.}=6.0{\times}10^{-6}$ > $W(dcq)_4;k_{obs.}=6.4{\times}10^{-6}$ > $W(dcq)_2(mpd)_2;k_{obs.}=7.0{\times}10^{-6}$ > $W(dcq)_1(mpd)_3;k_{obs.}=1.7{\times}10^{-5}$, which showed the inertness until 16days, 10days, 9days, 8days, and 4days. The $W(mpd)_4$ is very inert as $k_{obs.}=3.6{\times}10^{-6}$(16days) in xylene at $90^{\circ}C$ and $k_{obs.}=6.0{\times}10^{-6}$(10days) in DMSO at $90^{\circ}C$.

• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.5 no.3
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• pp.195-207
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• 2000

Organic and inorganic characteristics including bacterial cell number, enzyme activity, nutrients, and heavy metals have been monitored in twelve acrylic experimental tanks for two weeks to estimate and compare self-purification capacities in two Korean wet-land environments, tidal flat and rice field, which are possibly different with the environments in other countries because of their own climatic conditions. FW tanks, filled with rice field soils and fresh water, consist of FW1&2 (with paddy), FW3&4 (without paddy), and FW5&6 (newly reclaimed, without paddy). SW tanks, filled with tidal flat sediments and salt water, are SW1&2 (with anoxic silty mud), SW3&4 (anoxic mud), and SW5&6 (suboxic mud). Contaminated solution, which is formulated with the salts of Cu, Cd, As, Cr, Pb, Hg, and glucose+glutamic acid, was spiked into the supernatent waters in the tanks. Nitrate concentrations in supernatent waters as well as bacterial cell numbers and enzyme activities of soils in the FW tanks (except FW5&6) are clearly higher than those in the SW tanks. Phosphate concentrations in the SW1 tank increase highly with time compared to those in the other SW tanks. Removal rates of Cu, Cd, and As in supematent waters of the FW5&6 tanks are most slow in the FW tanks, while the rates in SW1&2 are most fast in the SW tanks. The rate for Pb in the SW1&2 tanks is most fast in the SW tanks, and the rate for Hg in the FW5&6 tanks is most slow in the FW tanks. Cr concentrations decrease generally with time in the FW tanks. In the SW tanks, however, the Cr concentrations decrease rapidly at first, then increase, and then remain nearly constant. These results imply that labile organic materials are depleted in the FW5&6 tanks compared to the FW1&2 and FW3&4 tanks. Removal of Cu, Cd, As from the supernatent waters as well as slow removal rates of the elements (including Hg) are likely due to the combining of the elements with organic ligands on the suspended particles and subsequent removal to the bottom sediments. Fast removal rates of the metal ions (Cu, Cd, As) and rapid increase of phosphate concentrations in the SW1&2 tanks are possibly due to the relatively porous anoxic sediments in the SW1&2 tanks compared to those in the SW3&4 tanks, efficient supply of phosphate and hydrogen sulfide ions in pore wates to the upper water body, complexing of the metal ions with the sulfide ions, and subsequent removal to the bottom sediments. Organic materials on the particles and sulfide ions from the pore waters are the major factors constraining the behaviors of organic/inorganic elements in the supernatent waters of the experimental tanks. This study needs more consideration on more diverse organic and inorganic elements and experimental conditions such as tidal action, temperature variation, activities of benthic animals, etc.