Coulometric Determination of Iridium in Fluoride and Chloride Solutions

The electrochemical behavior of iridium fluoride complexes formed through the oxidation of iridium metal with BrF₃in 0.6 M HCl was studied by cyclic voltammetry and controlled-potential coulometry using a platinum electrode. A procedure was proposed for the direct coulometric determination of iridium in solutions after sample fluorination. The procedure was used for the analysis of iridium concentrates.     

A microprocessor-aided modified Simons' reactor system for electrochemical fluorination processes

A modified Simons' reactor system has been developed for electrochemical fluorination processes. This reactor employs batch mixer design criteria to enhance and enable the characterization of the mass transfer in the reactor. Four monopolar packs of electrodes, each comprised of two nickel anodes sandwiched between three nickel cathodes, were used. A more uniform anodic current density distribution was achieved and the electrode packs were oriented to serve as baffles for the mixed flow field.A custom designed and fabricated, Motorola 6800 based, microprocessor system in conjunction with an IBM Personal Computer and other accessories are employed for data acquisition, monitoring and control of the process.The uniqueness of the design and operational characteristics of this microprocessor-aided modified Simons' Reactor System will be discussed.     

Use of Fluorination Reactions in the Electrode Crater for Lowering the Detection Limits and Increasing the Reliability of the Direct-Current Arc Atomic Emission Determination of Elements

The formation of volatile fluorides of nonvolatile elements in the presence of the fluorine-bearing additive ZnF₂ in the electrode crater of a direct-current arc was confirmed experimentally. It was shown that the use of fluorination reactions in the electrode crater lowers the detection limits of hardly volatile elements in aluminum and zirconium oxides by 1–1.5 orders of magnitude. It was also shown using the analysis of fullerene as an example that fluorination reactions can be used to standardize the procedures for determining impurities in different matrices similar in composition and temperature parameters using the same reference samples.     

Flow electrochemistry: a safe tool for fluorine chemistry

The heightened activity of compounds containing fluorine, especially in the field of pharmaceuticals, provides major impetus for the development of new fluorination procedures. A scalable, versatile, and safe electrochemical fluorination protocol is conferred. The strategy proceeds through a transient (difluoroiodo)arene, generated by anodic oxidation of an iodoarene mediator. Even the isolation of iodine(iii) difluorides was facile since electrolysis was performed in the absence of other reagents. A broad range of hypervalent iodine mediated reactions were achieved in high yields by coupling the electrolysis step with downstream reactions in flow, surpassing limitations of batch chemistry. (Difluoroiodo)arenes are toxic and suffer from chemical instability, so the uninterrupted generation and immediate use in flow is highly advantageous. High flow rates facilitated productivities of up to 834 mg h⁻¹ with vastly reduced reaction times. Integration into a fully automated machine and in-line quenching was key in reducing the hazards surrounding the use of hydrofluoric acid.

A scalable, efficient and safe electrochemical fluorination protocol is conferred. A broad range of iodine(iii) mediated transformations were performed in high yields without exposure to toxic HF.     

Electrochemical fluorination of methanedisulfonyl fluoride

The electrochemical fluorination of methanedisulfonyl fluoride in anhydrous hydrogen fluoride to produce difluoromethanedisulfonyl fluoride, a precursor of difluoromethane disulfonic acid, was investigated. This study was carried out in a microprocessor-aided modified Simons' reactor system at constant anodic potential using a Cu/CuF₂ reference electrode. Product yields of 75–82%, current efftciencies in excess of 66%, and electrical energy efficiencies of at least 33% were obtained for the electrochemical fluorination step.Experimental results of this investigation are presented and discussed.     

Prevention of anode fouling during the electrochemical perfluorination of aromatic carboxylic acid chlorides

The electrochemical perfluorination of benzoyl chloride, p-substituted benzoyl chlorides and cyclo-hexane carboxylic acid chloride in anhydrous hydrogen fluoride (AHF) medium on nickel electrode is reported. Experimental conditions suppressing polymeric film formation on the electrode are optimized. Addition of 1 wt.% dimethyl sulfide based on the volume of AHF in the initial stage of electrochemical fluorination and maintenance of the reactant and intermediate concentrations below a critical level ensured electrochemical fluorination of all the reactants without fouling of the electrode surface. Presence of p-substituents in the benzene ring improved the selectivity of alicyclic perfluoro carboxylic acid. GC/MS and ¹⁹F NMR data for the major perfluorinated products are reported.     

Electrophilic fluorination with N,N′-difluoro-2,2′-bipyridinium salt and elemental fluorine

N,N′-Difluoro-2,2′-bipyridinium bis(tetrafluoroborate) (MEC-31) was shown to be a highly reactive electrophilic fluorinating agent with the highest effective fluorine content in its class. We have developed the perfect recycled fluorination system with MEC-31 for the lower-cost industrial fluorination and for an environment. MEC-31 can be completely recycled including the counter-anion. We found the fluorination of 2-naphthol in liquid CO₂ with MEC-31 in the presence of catalytic amount of NaOTf proceeded quantitatively without the generation of by-product.

In the fluorination of 1,3-dicarbonyl compounds with elemental fluorine, we found the introduction method of fluorine gas would be very important in order to make a reaction efficient. As fluorination goes on, the quantity of 1,3-dicarbonyl compounds of the starting material is reduced gradually, and therefore the quantity of fluorine must be reduced by the method to control the flow rate or the concentration of fluorine gas diluted with nitrogen, together the fluorination to proceed efficiently.     

纺丝组件砂腔中流体流动性的冷态模型研究

自制冷态模型实验装置,针对熔融纺丝组件中的流体流动特征进行研究。实验结果表明:利用葡萄糖浆溶液作为PA6熔体的模拟介质是可行的,糖浆粘度与PA6熔体粘度有相似的变化规律及一定条件下粘度值相近,糖浆粘度随着剪切速率的增加而出现剪切变稀现象;在温度为21℃时,糖浆粘度与265℃时PA6熔体粘度接近,表明常温下,用糖浆作为模拟介质是可行性的;通过模拟介质在透明纺丝组件中流动特性的研究表明:流体在纺丝组件的砂腔中流动并不是理想的平推流,在压盖下方物料停留时间较四周长,不利于物料性质的均匀性。此研究实验结果为优化纺丝组件奠定了一定的基础。     

Electrochemical fluorination using porous nickel and foam nickel anodes

This work set out to examine the reasons behind some of the problems associated with ECF, namely, lack of reproducibility, low chemical yields, poor selectivity and low current densities, with a view to ameliorating these shortcomings and making the process more attractive to the chemical industry.The approach was to study the chemistry under controlled conditions of potential, reactant concentration, temperature, etc., and to analyse the results in terms of product structure, distribution and yield.Two distinct stages in the process were identified, i) the conditioning of the electrode, and, ii) the fluorination of the organic substrate.These stages are described in detail in relation to two model systems investigated, the fluorination of propene using porous and foam nickel anodes, and the fluorination of the octanoyl chloride using nickel foam anodes. The scales of experiments ranged from 100ml to 100 1 cell capacities.General conclusions are derived and recommendations made for the more efficient operation of the process.     

Application of a New pH‐Sensitive Electrode as a Detector in Flow Injection Potentiometry

A new pH sensitive detector for flow‐through potentiometry was developed on the basis of a graphite/quinhydrone composite electrode. The detector was constructed of two polymethylmethacrylate plates between which a 0.1 mm thick sensitive layer is situated. After drilling a hole through the plates, a ring of the sensitive layer is exposed to the solution stream. A conventional calomel reference electrode was placed downstream following the flow‐through sensor. The response behavior in different electrolyte solutions was investigated. The detector shows a Nernstian behavior for injections of hydrochloric acid into a KCl background solution as well as for the steady state response in concentration step experiments using hydrochloric acid and buffer solutions. The response time is sufficiently short for FIA applications (T₉₅ between 3 and 5.4 s). The influences of flow rate and injection volume on the detector signal are discussed.     

Impacts of fluorine on the electrochemical properties of Li[Ni0.5Mn0.5]O2 and Li[Li0.2Ni0.15Co0.1Mn0.55]O2

The impact of the fluorine substitution on the electrochemical properties of layered lithium nickel manganese positive electrode materials for lithium ion batteries is summarized. The addition of a controlled amount of fluorine to the oxygen lattice can effectively improve the capacity retention as well as reduce the impedance of the positive electrode materials. The fluorination of the nickel and manganese based layered oxide cathode material has also led to significant improvement in cycle life and power capability of the battery.     

A Self‐Sampling‐and‐Flow Biosensor for Continuous Monitoring

A self‐sampling‐and‐flow biosensor was fabricated by sandwiching a nitrocellulose strip on the working electrode side of the double‐sided microporous gold electrodes and a wicking pad on the counter electrode side. The double‐sided microporous electrodes were formed by plasma sputtering of gold on a porous nylon substrate. Sample was taken up to the enzyme‐immobilized working electrode by the capillary action of the front nitrocellulose strip dipped into the sample solution, analyzed electrochemically at the enzyme‐immobilized electrode, and diffuses out to the backside wicking pad through the micropores of the electrodes, constituting a complete flow cell device with no mechanical liquid‐transporting device. Biosensor was formed by co‐immobilizing the glucose oxidase and electron transfer mediator (ferrocene acetic acid) on the thioctic acid self‐assembled monolayer‐modified working electrode. A typical response time of the biosensor was about 5 min with the sensitivity of 2.98 nA/mM glucose, providing linear response up to 22.5 mM. To demonstrate the use of self‐sampling‐and‐flow biosensor, the consumption rate of glucose in the presence of yeast was monitored for five days.     

Fluorination effect of activated carbon electrodes on the electrochemical performance of electric double layer capacitors

The surface of phenol-based activated carbon (AC) was fluorinated at room temperature with different F₂:N₂ gas mixtures for use as an electrode material in an electric double-layer capacitor (EDLC). The effect of surface fluorination on EDLC electrochemical performance was investigated. The specific capacitance of the fluorinated AC-based EDLC was measured in a 1 M H₂SO₄ electrolyte, in which it was observed that the specific capacitances increased from 375 and 145 F g⁻¹ to 491 and 212 F g⁻¹ with the scan rates of 2 and 50 mV s⁻¹, respectively, in comparison to those of an unfluorinated AC-based EDLC when the fluorination process was optimized via 0.2 bar partial F₂ gas pressure. This enhancement in capacitance can be attributed to the synergistic effect of increased polarization on the AC surface, specific surface area, and micro and mesopore volumes, all of which were induced by the fluorination process. The observed increase in polarization was derived from a highly electronegative fluorine functional group that emerged due to the fluorination process. The increased surface area and pore volume of the AC was derived from the physical function of the fluorine functional group.     

Miniaturized thin-layer radial flow cell with interdigitated ring-shaped microarray electrode used as amperometric detector for capillary electrophoresis

A chip-type thin-layer radial flow cell was developed as an amperometric detector for capillary electrophoresis. We fabricated a carbon film-based interdigitated ring-shaped array (IDRA) microelectrode with a 2 microm bandwidth and an almost 1 microm gap on a glass plate and used it as a working electrode. A fused-silica capillary was arranged above the IDRA electrode using a guide hole drilled through the acryl plate that formed the flow cell lid. A flow channel for use in connecting the outlet capillary was also fabricated in the acryl plate. We characterized the analytical performance of the IDRA electrode in the microchip flow cell in terms of linear concentration range, sensitivity and concentration detection limit. We achieved a collection efficiency and catechol redox cycle at the IDRA microelectrode of 65% and 1.71, respectively, and thus a high sensitivity and low detection limit of 392.9 pA/microM and 15 nM for dopamine hydrochloride. We examined the reproducibility of the detector and found that the run-to-run and detector-to-detector relative standard deviations were both less than 10%.     

An enzyme reactor electrode for urea determinations.

An enzyme reactor electrode system for the determination of urea is described. A buffer is pumped through an enzyme reactor (0.4 ml) containing urease immobilized with glutaraldehyde to glass. The effluent is mixed with sodium hydroxide pumped through a second channel and fed through an ammonia gas electrode. Samples are introduced via a third flow channel and mixed with the buffer. The conversion of urea to ammonia is quantitative for sample concentrations of less than 0.03 M for a flow rate of 40 ml h^-1. The reactor electrode shows a Nernstian slope of 57 mV/decade for 5·10^-5–3·10^-2 M urea. The response is independent of variations in the flow rate, enzyme activity or temperature of the reactor.     

氩氧控制气氛下直流电弧放电中氟化反应

本文以前文为基础测定了不同氟化剂存在下杂质元素的蒸发率,计算了弧温、电子密度以及杂质元素的电离度,研究了影响元素谱线强度的诸因素,用晶体X射线衍射分析了电极反应残留物,提出了氟化反应的机理,并通过热力学计算予以说明。 1实验部分 1.1 仪器及主要工作条件 HILGER WATTS大型棱镜摄谱仪,直流电弧光源,电流10     

Determination of sulfite in beer samples using an amperometric fill and flow channel biosensor employing sulfite oxidase

A simple method is described to determine sulfite in beer samples using a fill and flow channel biosensor. A droplet of sample is placed into the inlet of a rectangular flow cell and begins to flow through the channel by capillarity. The flow is maintained and controlled by a porous outlet plug of defined porosity. In a rectangular flow cell, the sample solution flows through three consecutive zones: over a predictor electrode, an enzyme layer and a detector electrode. Together these three zones enable the differentiation between current due to sulfite and current due to other electroactive species in the sample. The predictor electrode is located upstream, and on the opposite channel wall to the enzyme layer and detector electrode, and is poised at the same potential (+0.65 V versus Ag/AgCl) as the detector electrode. On this electrode, the current contribution from all species in the sample solution that are oxidized at that potential is determined. The enzyme layer contains sulfite oxidase, which, in the process of oxidizing sulfite, produces hydrogen peroxide, which itself is reduced by excess sulfite. The current at the downstream detector electrode is therefore different from that at the predictor electrode as a result of the enzyme reaction and the difference of the currents, corrected for the dimensions of the electrodes, is proportional to the concentration of sulfite. The method enables a straightforward correction of the interfering current at the detector electrode and a determination of the analyte concentration. The effect of interferences from ascorbic acid, ethanol, sorbic acid and tartaric acid in the detection of sulfite is efficiently removed. The concentration of sulfite in a sample of beer measured by the biosensor is equivalent to that measured using a reference method based on the AOAC-recommended Monier-Williams method.     

钴卟啉修饰碳纤维束葡萄糖酶微电极的研究

生物电化学传感器的微型化研究是目前生物传感器研究中的一个很活跃的方向。我们曾用钴卟啉修饰碳纤维柱电极,并以它为基底制成了葡萄糖微传感器。为加强电极的抗折断能力,本文把约1千支碳纤维(φ9μm)做成碳纤维束盘微电极,在其表面修饰四苯基钴卟啉后,以其为基底制成了葡萄糖酶电极。将其用于流动注射分析,可以大大提高线性响应上限。     

A new flow field design for polymer electrolyte-based fuel cells

We present a new flow field design, termed convection-enhanced serpentine flow field (CESFF), for polymer electrolyte-based fuel cells, which was obtained by re-patterning conventional single serpentine flow fields. We show theoretically that the CESFF induces larger pressure differences between adjacent flow channels over the entire electrode surface than does the conventional flow field, thereby enhancing in-plane forced flow through the electrode porous layer. This characteristic increases mass transport rates of reactants and products to and from the catalyst layer and reduces the amount of liquid water that is entrapped in the porous electrode, thereby minimizing electrode flooding over the entire electrode surface. We applied this new flow field to a single direct methanol fuel cell and demonstrated experimentally that the new flow field resulted in substantial improvements in both cell performance and operating stability as opposed to the conventional serpentine flow field design.     

The fluorination of Butane over cobalt trifluoride

The fluorination of butane over cobalt trifluoride has given a complex mixture of partially fluorinated compounds: 51 of these have been identified, comprising over 99% of the products. Most were polyfluorobutanes but 1-2% were polyfluoro-2-methylpropanes. The reaction has no synthetic utility. There was some selectivity in the fluorination: secondary C-H was converted into C-F more easily then primary, and the ease of replacement of a particular H was reduced by geminal and vicinal fluorines. A computer of the fluorination was only partially successful, perhaps because the fluorination proceeded in part by simple F for H replacement and in part via alkenes: the model only allowed for the former.