The ultraviolet photochemistry of N,N'-bis(salicylidene)ethylenediamine copper(II), Cu(sal)2en, was investigated with low pressure mercury lamp. Redution of Cu(Ⅱ) and formation of Cl- were shown on 254 nm irradiation both for aerated and deaerated chlorinated hydrocarbon solvent such as CH2Cl2, chloroform, and 1,2-dichloroethane. Relatively long lived $({\tau}=100{\mu}sec)$ intermediate was detected by flash photolysis. Overall photo-process can be described as the formation of Cl- and new copper complex, product(1) by chlorohydrocarbon mediation, photoinduced reduction by abstraction of halogen from solvent, followed by redox induced substitution of axial ligand with chlorine. Product(1) is possibly Cu(III) chlorosalicylaldeimido complex and cyclic -CH2CH2- moiety is absent in the structure. 247nm band of Cu(sal)2en should contain ligand to metal charge transfer character.

Catalytic effects of various Schiff base metal(II) complexes on the reduction of thionyl chloride at glassy carbon electrode are evaluated by determining the kinetic parameters from cyclic voltammetry technique. The charge transfer process is affected strongly by the concentration of catalysts during the reduction of thionyl chloride. The catalytic effects are shown by both a shift of the reduction potential for thionyl chloride toward more positive direction and an increase in peak current. The diffusion coefficient value, Do, of the 8.17 ${\times}$ 10-9 $cm^2/s$ was observed at the bare glassy carbon electrode, whereas larger values (0.9-1.09 ${\times}$ 10-8 $cm^2/s$) were observed at the catalyst supported glassy carbon electrode. Significant improvements in the cell performance have been noted in terms of both exchange rate constants and current densities at glassy carbon electrode.

The catalytic activities of palladium(0,Ⅰ,Ⅱ)-diphosphine complexes were investigated in styrene oxidation using H2O2 as terminal oxidant. The rates showed a dependence on the chelate ring patterns of complexes (PdCl2L); 5-membered ring (L=dppe: 1,2-bis(diphenylphosphino)ethane) < 6-membered ring (L=dppp: 1,3-bis(diphenylphosphino)propane) < 4-membered ring (L= dppm: bis(diphenylphosphino)methane). This sequence correlates with the ligand field strength and interactions between metal and phosphine ligands. Pd(Ⅱ,Ⅰ)-diphosphine complexes which are capable of making 4-membered chelate ring showed an enhancement of catalytic activities for styrene oxidation. The catalytic activities of Pd(0,Ⅰ,Ⅱ)-diphosphine complexes are described in terms of electronic and steric factors.

Passive films formed on chromium surface in citrate buffer solution were investigated by means of three-parameter ellipsometry. The citrate buffer was found to be a suitable medium in which oxide film on chromium could be removed by cathodic treatment, providing a reference surface for the optical study. The passive film effectively protecting the chromium surface from corrosion was found to have thicknesses in the range 0.65 to 1.25 nm depending on the potential in the range of -0.20 to 0.60 V (0.1M KCl calomel electrode). The complex refractive index of the passive film did not show significant potential-dependent changes, indicating that the composition of the film material does not depend on potential.

Axial coordination of anions or water to the square-planar nickel(Ⅱ) complexes of the hexaaza macrocyclic ligands 1, 2, and 3, which contain two extra uncoordinated tertiary nitrogens, have been investigated in aqueous solutions containing HX (X=Cl-, Br-, NO3-, or ClO4-) and/or NaX. The nickel(Ⅱ) complexes exist in the acidic solutions as equilibrium mixtures of the square-planar [Ni(L)]2+ (L=1, 2, and 3) and octahedral species [Ni(H2L)X2]2+ (H2L=diprotonated form of L). Some octahedral complexes have been isolated and characterized. The solution behaviors of the complexes indicate that the formation of the octahedral complexes are significantly promoted by the protonation of the uncoordinated tertiary amines. The proportion of the octahedral complexes depends on the type of acid, and increases in the order of HBr < HNO3 < HCl.

A method for determining nitrate in post treatment chromium plating solutions with PVC-based nitrate-selective electrodes is described. PVC-based nitrate-selective membranes which contain TDMANO3 ion-exchanger in PVC/NPOE, PVC/DOA or PVC/DBP matrices, and a commercially available Corning electrode (No. 476134) have been compared in respect of their detection limits, response slopes, selectivities at various pHs, and dynamic response to the hydrochromate ion in basic condition. The PVC/DBP/TDMANO3 membrane electrode was chosen as the ISE detector for the determination of nitrate in the presence of hydrochromate interference. The amount of nitrate in real post treatment chromium plating solution could be determined successfully with this electrode in both static and flow-injection measurements when the sample was properly diluted with an alkaline buffer.

The electronic structures of the C60, (H3P)2Pt(η2-C2H4) and (H3P)2Pt(η2-C60) are calculated by using the EHMO method with the fragment analysis. We have modified the EHT parameters so as to yield the orbital energy level correlation and to fit the optical transition gap to the previous theoretical results of C60. In Pt-derivatives, our FMO results with the modified parameters show that the carbon-carbon double bonds of C60 and ethene react like those of electron-poor arenes and alkenes, and also that C60 is more electron-susceptive than C2H4.

The absorption spectra of holmium nitrate and erbium nitrate and the difference absorption spectra of their complexes with crown ethers were measured in acetonitrile. The crown ethers used in this study are 12-crown-4 and 15-crown-5. The oscillator strengths for the 4f→4f multiplet-to-multiplet transitions are empirically determined from the absorption spectra in combination with the difference spectra. The intensity parameters Ωλ (λ=2, 4, 6) for the systems are also evaluated by applying the Judd-Ofelt theorem to the observed oscillator strengths. The values of the intensity parameters are compared and discussed to investigate the sensitivity of the intensity parameters to the ligand environment.

A pulsed molecular beam source having short pulse duration (typically 70 ${\mu}s)$ and narrow velocity distribution (${\Delta}$v/v=8% for helium) has been costructed utilizing a commercial fuel injector. Beam characteristics of helium and ammonia seeded in helium expansions are accomplished by the use of an electron impact time-or-flight mass spectrometer. The comparisons between experimental data and theoretical calculations show that the proper beam speed is important to predict the evolution of stream temperature and valve shutter function. The decreasing tendency of pulse duration with increasing cluster size leads to the conclusion that the cluster beam property is described as a function of cluster mass and disinct cluster temperature.

Single crystal EPR spectra of K12[As2W18O66Cu3(H2O)2]${\cdot}$11H2O exhibit an orientation-dependent fine structure of an S = 3/2 system which is accounted for by the exchange and magnetic dipole interactions among the three Cu2+ ions. The hyperfine structure and the lines from the S = 1/2 manifolds have not been observed. The isotropic exchange parameters determined from the magnetic susceptibility data at 5-300 K are J1 = J2 =-7.8 cm-1. The magnitude of J values suggests that the unpaired electrons on three Cu2+ ions interact through a sequence of six bonds involving two tungsten atoms and three oxygen atoms. The Cu-Cu distance, 4.37 $\AA$, determined from the EPR spectra is considerably smaller than the value from the X-ray crystal structure determination, 4.76 $\pm$ 0.03 $\AA$, indicating that the point-dipole model underestimates the dipolar interaction.

The crystal structure of Ba46-X, Ba46Al92Si100O384 [a= 25.297(1) Å], has been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd&bar{3}at 21(1) ℃. The crystal was prepared by ion exchange in flowing stream of 0.05 M Ba(OH)2 aqueous solution for 5 days. The crystal was then dehydrated at 380 ℃ and 2 × 10-6 Torr for 2 days. The structure was refined to the final error indices R1= 0.051 and Rw= 0.054 with 369 reflections for which I > 3σ(I). In this structure, all Ba2+ ions are located at the three different crystallographic sites: fourteen Ba2+ ions are located at site Ⅰ, the centers of the double six rings, two Ba2+ ions lie at site Ⅰ', in the sodalite cavity opposite double six rings(D6R's) and another thirty Ba2+ ions are located at site Ⅱ in the supercage. Two Ba2+ ions are recessed ca. 0.27 Å into the sodalite cavity from their three O(3) oxygen plane and thirty Ba2+ ions are recessed ca. 1.11 Å into the supercage from their three O(2) oxygen planes, respectively (Ba(1)-O(3) = 2.76(1) Å, O(3)-Ba(1)-O(3) = 180(0)°, Ba(2)-O(3) = 2.45(1) Å, O(3)-Ba(2)-O(3) = 108(1)°, Ba(3)-O(2)=2.65(1) Å, and O(2)-Ba(3)-O(2)=103.9(4)°).

Semiempirical MO calculations using the PM3 method are performed on the reactions of acetate esters with substituted phenolate anions. The mechanistic change from rate-limiting formation to breakdown of the anionic intermediate is shown to occur in the gas-phase, especially for meta-nitrophenyl acetate. However the mechanistic change-over takes place at a lower basicity ($pK_0$) of the anion nucleophile than found for the corresponding formate. This lowering of $pK_0$ has been ascribed to the electron donating effect of the methyl group in the acetate. For the reactions involving rate-limiting breakdown of the intermediate, the large Bronsted coefficients, ${\beta}_X({\beta}_{nuc})$, are expected in general, but the magnitude increases to a larger value and the pK0 is lowered accordingly, when an electron-donating nonleaving group, like $CH_3$, is present. This type of nonleaving group effect provides a necessary condition for the carbonyl addition-elimination mechanism with rate-limiting breakdown of the intermediate.

Laser induced fluorescence spectra of OH produced from photodissociation of $H_2O_2$ at 280-290 nm in the gas phase have been observed. By analyzing the Doppler profiles, the anisotropy parameter($\beta$ =-0.7) and the center of mass translational energy of the fragments have been measured. The measured energy distribution is well described by an impulsive model. The excited state leading to dissociation is found to be of 1Au symmetry. The dissociation from this state is prompt and direct with the fragment OH rotating in the plane perpendicular to the O-O bond axis.

A series of samples of the Nd1-x(Ba0.40Mg0.60)1+xFeO4-y (x=0.00, 0.10, 0.20, and 0.30) system has been synthesized at 1450 ℃ under an atmospheric air pressure. The x-ray powder diffraction analysis of the solid solutions assigns the structure of all the compositions to orthorhombic system. Mohr salt analysis shows that τ and y values increase with x value and nonstoichiometric chemical formulas of the system can be formulated from the x, τ, and y values. Oxygen vacancies are distributed along c-axis in the perovskite layer. The magnetic ordering temperature remains unchanged with x value. Electrical conductivity and activation energy depend only on the mixed valence state of Fe ion. Conduction mechanism can be suggested as the hopping of electron between eg orbitals of Fe3+ and Fe4+ ions through Fe3+-O-Fe4+ bonds. Magnetic susceptibility and electrical conductivity are discussed with the nonstoichiometric chemical formulas.

Complexation of ortho-xylyl-17-crown-5 (X17C5) with alkali metal ions in acetonitrile was studied by 7Li and 23Na NMR spectroscopy. The complex formation constants of X17C5 with LiI, LiSCN, NaI, and NaSCN were determined by investigating the changes in the chemical shifts as a function of the concentration ratio of X17C5 to metal ion. It was found that X17C5 forms 1:1 complex with Li+ and Na+ ions and the log Kf's for the complexation with LiI, LiSCN, NaI, and NaSCN were determined to be 2.88, 2.43, 2.53, and 2.30, respectively. In particular, the kinetics of complexation of X17C5 with Na+ was investigated by the method of 23Na NMR lineshape analysis. Activation energies were determined from Arrhenius plot of the resultant rate constant data to be 25.4 kJ/mol for NaI and 15.1 kJ/mol for NaSCN. Other kinetic parameters were also calculated by employing the Eyring equation. The decomplexation rates measured were 1.82 × 104 M-1s-1 for NaI and 1.50 × 104 M-1s-1 for NaSCN. It is concluded that the decomplexation mechanism is predominantly a bimolecular cation exchange for both cases.

A topological theory has been introduced to extend the theory of Balsara and Nauman to evaluate the entropy of in homogeneous polymer solutions. Previous theories have considered only the terms about the displacement of junction points, while the present theory has obtained a more complete expression for the entropy by adding the topological interaction terms between strands. There have been predicted the characteristics of the spinodal decomposition and the interfacial tension of polymer solutions from the resultant expression. It is exposed that the theoretically predictive values show good agreement with the experimental data for polymer solutions.

The relationship between the signs of ${\rho}i(0)$, ${\rho}j(0)$ and ${\rho}ij$ and validity of the reactivity-selectivity principle (RSP) has been derived: RSP is valid when W = ${\rho}i(0){\cdot}{\rho}j(0)/{\rho}ij$ is negative. The analysis of 100 reaction series indicated that for normal SN2 reactions involving variations of substituents in the nucleophile (X) and in the substrate (Y) RSP is valid only for a dissociative type for which ${\rho}Y(0)$ is negative, whereas for the acyl transfer reactions with rate-limiting breakdown of the tetrahedral intermediate RSP is valid in general for all substituent changes, X, Y and/or Z (substituent on the leaving group). The trends in the validity of RSP for certain types of reaction can be useful in supplementing the mechanistic criteria based on the signs of ${\rho}i(0)$, ${\rho}j(0)$ and ${\rho}ij$.

The visible emission spectra of the o-xylyl radical in the gas phase have been obtained using a Fourier transform spectrometer coupled with a technique of supersonic expansion. The o-xylyl radical was generated in a jet by expansion with an inert buffer gas He from a high voltage dc discharge of the precursor o-xylene. The spectra were analyzed on the basis of the rotational contours of the vibronic bands as well as the known vibrational frequencies by a matrix isolation method.