ATTEMPTS TO MODIFY AN ELECTRODE WITH A CONDUCTING PLATINUM CLUSTER COMPOUND

A conducting platinum cluster compound K1.64Pt(C2O4)(2) was electrochemically synthesized on a glassy carbon electrode through the electrooxidation of K2Pt(C2O4)(2) in an aqueous medium using single potential step and cyclic voltammetry methods. The precursor K2Pt(C2O4)(2) was prepared by a ligand exchange reaction between C2O42- and PtCl42-. During single potential step experiments, the electrolytic current corresponding to the oxidation of K2Pt(C2O4)(2) increased dramatically after a sharp decrease at the beginning (due to the formation of conducting K1.64Pt(C2O4)(2) on the surface of the working electrode). Two kinds of mechanism account for the current transients at the different applied potentials. Cyclic voltammetry was conducted with K1.64Pt(C2O4)(2) on the surface of the working electrode and a steady-state diffusion current was observed. Since the material grew in a fibrous manner, each conducting fiber which was in contact with the electrode could serve as an ultramicroelectrode. The behavior of the working electrode was thus changed from a plain to an ultramicroelectrode array.

THERMODYNAMICS OF AMINO-ACID DISSOCIATION IN MIXED-SOLVENTS .3. GLYCINE IN AQUEOUS GLUCOSE SOLUTIONS FROM 5-DEGREES-C TO 45-DEGREES-C

The first thermodynamic dissociation constants of glycine in 5, 15 mass % glucose + water mixed solvents at five temperatures from 5 to 45-degrees-C have been determined from precise emf measurements of a cell without liquid junction using hydrogen and Ag-AgCl electrodes and a new method of polynomial approximation proposed on the basis of Pitzer's electrolytic solution theory in our previous paper. The results obtained from both methods agree within experimental error. The standard free energy of transfer for HCl from water to aqueous mixed solvent have been calculated and the results are discussed.

SPECTROELECTROCHEMISTRY WITH CYLINDRICAL CARBON-FIBER MICROELECTRODES

Transmittance spectroelectrochemistry can be performed using a group of cylindrical microelectrodes. A dependence of absorbance on electrolytic charge during the potential step was derived. The rate constant of catalytic reaction of the ferrocyanide-ascorbic acid system was determined using single potential step-open circuit relaxation chronoabsorptometry. This is the first report that the reaction can still be considered as a pseudo-first-order reaction when the concentration of ascorbic acid is close to and even slightly lower than the concentration of ferrocyanide. The determined rate constant is in agreement with the reported value. The reason is that the diffusion of ascorbic acid toward electrode surface is contractive and the diffusion of the electrogenerated ferricyanide from the electrode surface to the bulk of solution is expansive.

Hydrogen permeation behavior and corrosion monitoring atmospheric of steel in cyclic wet-dry environment

Hydrogen permeation of 16Mn steel under a cyclic wet-dry condition was investigated by Devanathan-Stachurski's electrolytic cell with a membrane covered on the exit side by a nickel layer and the weight loss was measured for each wet-dry cycle. The results show that hydrogen permeation current change with different atmospheric environment: distilled water, seawater, and seawater containing 100 ppm H2S. The results show that seawater can induce an increase in the hydrogen permeation current due to the hydrolyzation reaction. And after the increase, equilibrium is reached due to the equilibrium of hydrolyzation reaction effect and the block of the rust layer. On the other hand, H2S contamination also can induce an increase in the maximum hydrogen permeation current due to the hydrolyzation reaction. And H2S contamination delays the time that hydrogen permeation is detected because of the formation of the FeS(1-x) film. The FeS(1-x) film can block the absorption of hydrogen onto the specimen surface. The surface potential change and the pH change of the metal surface control the hydrogen permeation current. And a clear linear correlation exists between the quantities of hydrogen permeated through the 16Mn steel and the weight loss. Based on the linear correlation, we monitored the corrosion rate by monitoring the hydrogen permeation current by a sensor outside. Good coherences were shown between results in laboratory and outside.

The hydrogen permeation investigation of API X56 steel in sea mud

It was found that the corrosion rate of steel in the sea mud with sulfate-reducing bacteria (SRB) could be as high as 10 times of that in the sea mud without SRB. And the hydrogen permeation reaction would occur when metals were corroded. So it is necessary to investigate the effect of living SRB on hydrogen permeation in the sea mud. Cathodic potential was often added to metals in order to protect them. But hydrogen permeation could be affected by the cathodic potential. So it is also necessary to study the effect of cathodic potential on hydrogen permeation. In this paper, the hydrogen permeation actions of APT X56 steel in the sea mud with and without SRB at corrosion and cathodic potential were studied with an improved Devanathan-Stachurski's electrolytic cell. Experimental results showed that during the growth of SRB, the current density curve of hydrogen permeation was accordant with the growth curve of SRB. But the hydrogen permeation current density of APT X56 steel hardly changed in the sterilized sea mud. Compared with the hydrogen permeation current density of APT X56 steel in the sterilized sea mud, the hydrogen permeation of APT X56 steel in the sea mud could be accelerated by living SRB. Experimental results also showed that the hydrogen permeation current density increased rapidly when the cathodic potential was added to the three-electrode system of the cathodic cell, and then the hydrogen permeation current density could obtain a stable value slowly. So the cathodic potential added to the cathodic cell could accelerate hydrogen permeation.

塔里木盆地塔中—巴楚地区早二叠世岩浆岩地球化学特征及其成因

Tazhong-Bachu region is located in the Western Tarim basin.The early Permian magmatic rocks occur in the earth surface of Tazhong-Bachu region are mainly distributed in Kepintag,Mazhartag and Wajilitag region. There are a lot of wells, in which researchers found the early Permian magmatic rocks,in desert cover area.Most magmatic rocks are basic rocks, a few of which are ultrabasic rocks and intermediate-acid magmatic rocks.The ultrabasic rocks are are mainly occur in the Cryptoexplosive Breccia Pipes ,which is located in the volcanic complex body of Wajilitag region.The basic rocks can be divided into three rock types：The first type of the magmatic rocks in Tazhong-Bachu region is volcanic rock ,which occurs in the Lower Permian Kupukuziman Formation and Kaipaizileike Formation. Most Volcanic rocks are basalts,a few of which are volcanic breccias and pyroclastic rocks.The basalts are distributed in stratiform occurrences and interbeded the clastic rocks in Kepintag region.The attitudes of the basalts are nearly horizontal.Columnar Joints, gas pore textures and amygdaloidal structure are to develop in basalts.The second type of the magmatic rocks in Tazhong-Bachu region is diabase,which occurs in Mazhartag region.Diabase dike swarms occur in the stratums of Silurian, Devonian, Carboniferous and Lower Permian.They make from NNW direction to SSE direction, the obliquity of stratum is greater than 60°, and the dike thickness is form several cm to several meters. Diabasic texture is found in the rocks .The first type of the magmatic rocks in Tazhong-Bachu region are gabbro- pyroxenite rocks ,which occur in the Wajilitag igneous complex body. The intermediate-acid magmatic rocks, which are mainly syenites, are located in Mazhartag and Wajiltag region. But they are small in the whole Tazhong-Bachu region.There are intermediate-acid magmatic rocks,which are mainly dacite,in the northeast part of the wells in Tazhong-Bachu region.But ,it is not found in earth surface.Through systematical geochemical research of early Permian magmatic rocks,which are distributed in Kepintag,Mazhartag, Wajilitag region and the wells such as F1 well、Z1 well、Z13 well、TZ18 well、H3 well、H4 well et al., the focus on the geochronologic characteristics, the main element,trace element and REE geochemistry, the mineralogic characteristics, the Sr-Nd and Pb isotopic characteristics are put forward. The main points are: 1、A combined study of CL imaging and LA-ICP-MS U-Pb dating were carried out for zircon grains of the magmatic rocks in the Tazhong-Bachu region from the Tarim basin.The results of the systematic zircon LA-ICP-MS U-Pb dating reveal 272±6Ma to 291±10Ma for the magamatic rocks. It indicated that Early Permian is an important period of magmatic acvivity in the Tazhong-Bachu region. 2、There are a big hunch in the curves of primitive mantle-normalized trace element concentrations in the early Permian magmatic rocks from Kepintag, Mazhartag, Wajilitag region and the 14 wells. Light rare earth elements are comparatively rich and heavy rare earth elements are comparatively poor. The slope rates are same between light rare erath elements and heavy rare earth elements. It is not like the curves of the basalts in the convergent margin of plate , in which the slope rates of light rare erath elements is bigger than the alope rates of heavy rare erath elements, and the curves of heavy rare earth elements are comparatively flat. The magmatic rocks of Tazhong-Bachu region rarely have the characteristics of the basalts in the convergent margin of plate, which is that Tantalum, Niobium and Titanium are much poor, and Zirconium, Hafnium and Phosphorus are moderately poor. The magamatic rocks are mostly alkaline, which is indicated by the dots of the (Na2O+K2O)-SiO2 identification diagram. All of these indicate that the early Permian magmatic rocks were formed in an extension environment of intraplate. 3、The Thorium abundance is high and Tantalum abundance is low in most magmatic rocks from Tazhong-Bachu reguion, which is formed for crustal contamination.In the Th/Yb-Ta/Yb identification diagram，most dots are in the region, which means active continental margin, but a few dots are in the region, which means mantle source. It indicated the feeding of continental crust materials. 4、The magnesium content of the olvines from Wagilitag region is richest, and the olvines from Kepintag region is poorest in the tree region. 5、Through the the Sr-Nd and Pb isotopic study of the basalts and diabases from the F1 well core, Z1 well core, Z13 well core,TZ18 well core, and the basalts，gabbros, diabases(diabase-prophyrites) and pl-peridotites from Kepintag,Mazhartag, Wajilitag region , it indicated that all isotopic data is similar and close to enriched mantle.