The kinetics of electrooxidation of HCOOH on Pt(100) via reactive intermediates was studied by using programmed potential step technique, which avoided successfully the interference of self-poisoning. A new data processing method was established based on the transform of integration of digital data recorded in electrochemical transient experiments, and the computer software developed for this method allowed us to obtain quantitatively, for the first time, the kinetics parameters of HCOOH oxidation on Pt(100) electrode. The results demonstrated that in a narrow potential range of 0.02 V to 0.15 V, the rate constant kf being varied from 9.510 × 10-4 to 1.38 ×10-2cm•s- 1 and the relationship between ln(kf) and E being a straight line. The transfer coefficient (β) was calculated at 0.309, and the diffusion coefficient (D) of HCOOH in 5×10-3mol•L- 1 HCOOH + 0. 5mol•L- 1 H2SO4 solution was evaluated at 1.80 × 10-5 cm2•s-1.

Intramolecular photoinduced electron transfer in a series of donor-acceptor systems consisting of 9,10-dimethoxyanthracene and differently substituted benzoic esters have been investigated. From fluorescence life-time measurements using single-photon counting technique, the rate constants of electron transfer ket were obtained. The free energy changes ΔG of electron transfer from the first excited state of 9,10-dimethoxyanthracene were obtained by determining the redox potentials of the donor and the acceptors and the first excitation energy. The dependence of photoinduced electron transfer rates on the exothermicity of the reaction has been studied by the theoretical analysis based on quantum mechanical treatments of electron transfer. The results show that the experimental values coincide well with that obtained by theoretical calculations. Although the inverted region is not seen in our results, the present treatment predicts that the inverted region would be observed at still lower values of ΔG than so far examined.

This paper studies theoretically the effect of circularly polarized laser on ESR spectra in a spin specie system. The antisymmetric polarizability and the laser-induced ESR shift (Δv -- Δv+) of the complex [IrBr6]2- were calculated. The influence of the width г of the absorption line on the ESR shift was discussed. The results show that the ESR shift can be as large as 1MHz order of magnitude at a frequency near optical absorption, which is similar to that of the sodium atom.

By using high-resolution solid state Nuclear Magnetic Resonance spectrometer with 27Al and 29Si probes, the interaction between Mo species and HZSM-5 of Mo/HZSM-5 catalysts has been studied. The results show that there is a strong interaction between Mo species and HZSM-5zeolite. The framework aluminum in the zeolite can be easily extracted by the introduction of Mo species. The extract ability of framework aluminum by Mo species increases with increasing Mo loading and the calcination temperature. The extraction process leads to the formation of non-framework Al at first and then a new crystalline phase of Al2(MoO4)3. The catalyst, therefore, lost its catalytic activity for methane dehydrogenation and aromatization in the absence of oxygen. The MAS NMR results give us an evidence that Al2(MoO4)3 crystallites are much less active for the reaction.

YBa2Cu3Ox(YBCO, x=6-7) thin films have been prepared on the YSZ substrate and studied for CO adsorption and hydrogenation by using XPS, XRD, and in-situ FTIR. The results showed that CO adsorption occured at Cu sites and react with the oxygen species in YBCO, resulting in the formation of adsorbed CO2 or -COO bonding species and oxygen vacancies in YBCO, therefore, the Cu2+ ions of YBCO are reduced to Cu+ or Cu0, and the orthorhombic structure of YBCO is transformed to the tetra nal phase. The oxygen vacancies are in favor of adsorption of CO, CO2, and H2. The main products of CO, CO2 hydrogenation are found to be CH3OH,CH3OCH3 and a trace of CH4, and the reaction intermediates might be aldehyde, formate and methoxy radical.

A novel al rithm is outlined for the variational quantum Monte Carlo treatment of molecules. The quantum Monte Carlo method is combined organically with the conventional Hartree-Fock method in the al rithm. An analytical expression of the local energy is presented. A new form of trial wavefunction and a new generator of random numbers is also used. This new al rithm is used to compute the energies of the ground states for molecules H2, LiH, Li2, H2O,F2 and the states X3B1 and a1A1 of CH2, and calculated results show that this novel al rithm is much superior to the usual VMC in both accuracy and statistical error.

In this paper a new method is presented for estimating thermodynamic properties of binary intermetallic compounds through fitting a simple correlation equation. Entropies and heat capacities of some binary intermetallic compounds are calculated by this new method. The result shows that this method is simple, and it can guarantee an acceptable accuracy.

Electrochemical reduction of oxygen on the La0.8Sr0.2MnO3/YSZ electrode has been investigated in detail with methods of Low Field Polarization , Cyclic Voltammetry and Potential Step. The results demonstrate that the reduction of oxygen on the LSM+YSZ cathode takes place through two pathways: at low temperatures oxygen reduction takes place at Three Phase Boundary (TPB), in which case the rate determining step is the diffusion of atomic oxygen from the LSM surface to TPB, while at high temperatures the reaction area extends over the whole surface of the LSM electrode and the rate determining step is the charge transfer step. It has also been found that the formation of oxygen vacancy is affected by reaction temperature, oxygen pressure and cathodic potential applied. Oxygen vacancy plays an important role in the electrochemical reduction of oxygen at high temperatures and high oxygen partial pressures.

An associating MH equation of state (AMH EOS) is developed on the basis of the MH equation of state by incorporating the chemical association into it, a constant evaluation method is proposed for the AMH EOS. The AMH EOS is used to calculate thermodynamic properties of water, some alcohols and carboxylic acids, od results are obtained. It shows that the constant evaluation method is feasible.

The multiphoton ionization spectra of ethylamine and dimethylamine are presented in the 400-470nm region, with resonance excitation to 3s Rydberg state. The MPI fragmentation patterns of two C2H7N isomers are readily distinguished. For ethylamine, the most prevalent fragmentation is β-Cleavage, while for dimethylamine that is H atom ejection.

The equation of state for aqueous electrolytes based on perturbation theory is established. By using the water molecular parameters and Pauling diameters of canons and anions without any additional parameters, the densities of 9 aqueous electrolyte systems (NaCl, CaCl2,KCl, LiCl, BaCl2, MgCl2, NaBr, Na2SO4 and MgSO4) at high pressure and temperature are predicted. The predicted accuracy of densities is satisfactory. The accuracy can be improved by using the fitted canon diameter instead of Pauling diameters.

For preparing O/W miniemulsions containing soybean oil and silicone oil, three methods, phase inversion emulsification, D-phase emulsification, reformed D-phase emulsification were tested by using Brij92, 97, 98 and Tween 80, 85, 60, 20 and Span 80, 60 mixed surfactants. It was found that the O/W miniemulsions of soybean oil and silicone oil can not be formed by phase inversion emulsification method, but can be formed by the two other methods. The results of emulsification showed that if gel emulsion, in which fine oil droplets disperse in continuous phase with high surfactant content, appears during the emulsification process, the O/W miniemulsions can be formed by simply diluting with water.

The interaction of methyl β-CD with cetyltrimethylammonium bromide in aqueous solution was investigated by twisted intramolecular charge transfer(TICT) dual fluorescence of sodium diethylaminobenzoate. It was shown that an 1: 1 CTAB / methyl β-CD inclusion complex was formed in CTAB and methyl β-CD mixed aqueous solution ,and this inclusion complex formed aggregates incorporated by CTAB. Electric conductivity measurements provided further support for this conclusion.

A method of preparation of stable, homogeneous and controlled thickness TiO2 film through hydrolysis of Ti(OC4H9)4 is introduced in detail. The structure and property of the film have been investigated by means of SEM and FT-IR techniques. The strong quenching effect between sensitizing dyes and TiO2 film is observed in their fluorescence spectra.

The thermal denaturation of the rice mitochondrial DNA in different solutions have been studied by using ultraviolet absorption spectrometry at 50 ℃, and their kinetic behaviour of the thermal denaturation has been discussed. The kinetic curves of the thermal denaturation of rice mitochondrial DNA in different solutions have been obtained, and the kinetic parameters and models have been calculated and established respectively.