• Bulletin of the Korean Chemical Society
• /
• v.11 no.4
• /
• pp.276-281
• /
• 1990

The equivalent conductance of univalent cation (potassium, silver, thallium and ammonium) perchlorates in methanol containing 18-membered crown ethers, 18-crown-6 (18C6) and 1,10-dithia-18-crown-6 (DT18C6) were measured at different temperatures. The equivalent conductances of ammonium perchlorate were increased by increasing content of DT18C6 exceptionally, due to more favorable solvations than complexations. From the equivalent conductance changes, the formation constants for 1:1 compmlexes have been determined, and the values of enthalpy and entropy changes have been calculated. The complexations of 18C6 and DT18C6 with the univalent cations under investigation are all exothermic and the ${\Delta}$S values are all negative and no considerable differences around 50 J/ (k mol). The selectivity order of 18C6 is $K^+ > Tl^+ > Ag^+ > NH_4^+$, while that of DT18C6 is $Ag^+ > Tl^+ > NH_4^+ > K^+$. By sulfur substitutions in 18C6 result in significant decrease in stability, but the stability of $Ag^+$-DT18C6 complex are $10^4$ times larger than those of $K^+$. This increase of stabilities for $Ag^+$-DT18C6 complex are primary due to the result of favorable exothermic heat of reaction between the polarizable soft cation and soft sulfur centers. In NMR experiment, the stepwise additions of cation perchlorates into crown ether solutions induced two major spectral changes. First, the resonance all shift down field and the cation induced shifts were linear up to 1:1 cation/crown ratio, above which no further changes were observed. On the basis of these results, it could be concluded that 1:1 complex is formed. Second, the magnitudes of cation induced shifts were different each other in same ligand. By addition of silver ion to the solution of DT18C6, the largest shift of proton peak near the sulfur atom was observed. These effects are also arisen from the results of covalent bonding between "soft-soft" interactions.

• Journal of Korean Society of Forest Science
• /
• v.111 no.3
• /
• pp.385-393
• /
• 2022

The study was carried out in Pocheon-si, Gyeonggi-do from March to December in 2019 to compare and analyze the water use strategies of two co-occurring tree species, Pinus densiflora and Quercus serrata, both native and dominant in Korea's forest ecosystems. Through seasonal changes, we measured environmental variables such as air temperature, relative humidity, precipitation, net radiation, and soil water content. Sap flow densities of P. densiflora (n = 6) and Q. serrata (n = 3) were measured, along with environmental variables. The maximum sa pflow density for Q. serrata almost doubled that of P. densiflora during the growing season, while the maximum sap flow densities in both Q. serrata and P. densiflora peaked in September and August, respectively. Net radiation and vapor pressure deficit, but not air temperature, were the major environmental variables significantly affecting sap flow density. Analysis of hysteresis revealed that P. densiflora exhibited isohydric behavior, while Q. serrata showed anisohydric behavior. Analysis of crown conductance revealed similar trends as sap flow density, i.e., the crown conductance of Q. serrata was twice that of P. densiflora during the growing period. The study compared and analyzed the water use strategies between two co-occurring species. To better understand the underlying mechanisms of water use, more research on both physiological and morphological traits are needed.

• Journal of the Korean Chemical Society
• /
• v.32 no.1
• /
• pp.53-59
• /
• 1988

Recently, the formation of the complexes between macrocyclic polyethers and alkali metal salts have been determined by several methods. It has been suggested that the specificity of the complexation be due to the nature of the surrounding solvent molecules. The formation constant values ($K_f$) of $K^+$ are shown to be the largest among the other alkali metal cations because the ionic diameter of $K^+$ is approximately the same with the hole size of 18-crown-6. In this study the formation constants of the 1 : 1 complexes of 18-crown-6 with potassium p-substituted phenoxide are calculated by the conductance measurement in organic solvents. As a result, the $K_f$ value series among organic solvents are given in the order of $CH_3$OH > DMF > DMSO. It seems that the donor number of the solvent is a main factor in the formation of the complex between $K^+$ metal ion and 18-crown-6 molecules. At the same time, the formation constants increase with increasing the electron-withdrawing power of substituents because the phenoxide ion is stabilized by the charge dispersion.