Programmable analyzer for voltammetric and chronopotentiometric experiments

A computerized system for voltammetric and chronopotentiometric analysis is described. The system consists of a microcomputerized electrochemical unit and a personal computer (PC) with peripherals. The eletrochemical unit is programmed and activated via a command list entered from the PC keyboard, and then operates independently. Meanwhile, the PC is available for data processing. The system can execute user-defined operations, e.g., voltage steps, measurement of relaxation current, at a frequency of 50 kHz in real time. Thus it affords a flexible means for implementation of standard as well as non-standard voltammetric techniques. The system facilitates a rapid comparison of voltammetric and chronopotentiometric techniques under analogous experimental conditions. Because electrode potentials can be sampled at a frequency as high as 660 kHz, the system is well suited for potentiometric stripping analysis of solutions with a high content of oxidants. The analytical possibilities of the instrument are demonstrated by two examples. In one, square-wave voltammetric and potentiometric stripping approaches are compared for the determination of traces of lead (II) in non-deaerated media. In the other, constant-current chronopotentiometry and square-wave voltammetry are compared for the quantitation of nickel (II) deposited by chemical interaction with a chemically modified electrode.     

Multiple-scanning potentiometric stripping analysis

A computerized data acquisition technique— multichannel potentiometric monitoring—is used in conjunction with potentiometric stripping analysis. Multiple-scanning stripping potentiograms can be recorded so that the analytical signals are enhanced. A minicomputer with an internal store of4K 16-bit words suffices for experimental control and data treatment. The technique is suitable for stripping analysis with preconcentration times of 60–90 s at a mercury film electrode with linear response ranges of 1–100 μg l^-1 for cadmium(II) and lead(II). For preconcentration times of 30 min, the limit of detection is about 5 ng l^-1. Preliminary tests on continuous flow analysis are reported.     

Potentiometric stripping analysis automation

A semi-automatic system for potentiometric stripping analysis (PSA) based on the use of a potentiostat, a pH-meter with RS232C interface, and a personal computer is described. The appropriate software developed allows automatic control of the pre-electrolysis time, data acquisition and manual or automatic data treatment. Several elements can be determined at ng/ml level.     

间断多次扫描电位溶出分析方法的研究

间断多次扫描电位溶出分析是在多次扫描电位溶出分析和间断扫描伏安法的基础上提出的一种新的电位溶出分析技术,它不仅具有多次扫描电位溶出分析灵敏度高的优点,又克服了多次扫描电位溶出分析对多元素分析时元素之间相互干扰的缺点。文章讨论了间断多次扫描电位溶出分析的实验条件,同时用这种方法分析了人尿中镉、铅的含量。间断多次扫描电位溶出分析在电积10分钟时,最低可检测到0.005ng/mL的镉和0.01ng/mL的铅。镉、铅浓度为4ng/mL时,相对标准偏差分别为2.9%和3.2%,证明间断多次扫描电位溶出分析可以同脉冲阳极溶出伏安法媲美。     

Stripping voltammetry for the determination of trace metal speciation and in-situ measurements of trace metal distributions in marine waters

Progress in marine chemistry has been driven by improved sampling and sample handling techniques, and developments in analytical chemistry. Consequently, during the last 20 years our understanding of marine trace metal biogeochemistry has improved a great deal. Stripping voltammetric techniques (anodic stripping voltammetry and adsorptive cathodic stripping voltammetry) have made an important contribution to this understanding. The selectivity and extremely low detection limits have made stripping voltammetry a widely used technique for trace metal speciation and trace metal distribution measurements in seawater. Stripping voltammetry is very suitable for ship-board and in-situ applications because of the portability, low cost and capability for automation of the voltammetric instrumentation. Future developments in stripping voltammetry can be expected in the field of stand-alone submersible voltammetric analysers, capable of continuous trace metal measurements. Future applications of stripping voltammetry can be found in the interactions between trace metal speciation and growth and the functioning of organisms in pristine and metal polluted marine waters.     

Sequential injection system with higher dimensional electrochemical sensor signals Part 1. Voltammetric e-tongue for the determination of oxidizable compounds

A sequential injection analysis (SIA) system was developed with the aim of obtaining an automatic and versatile way to prepare standards needed in the study of systems with higher dimensional sensor signals. To illustrate this, different analytical techniques were used in determinations of several analytes. Automated potentiometric calibrations of different potentiometric sensors, with and without interference, were carried out. Useful determinations of selectivity coefficients with two degrees of freedom were obtained. Simultaneous voltammetric determinations have also been done. Firstly, simultaneous determinations of lead and cadmium, using epoxy-graphite composite as the working electrode, have enabled a separate calibration for each metal to be obtained. Next, a voltammetric electronic tongue was designed and applied to the determination of oxidizable species. The use of artificial neural networks has solved the overlapped signal of ascorbic acid, 4-aminophenol and 4-acetamidophenol (paracetamol). A set of 63 data points was prepared automatically and has facilitated the training of an electronic tongue for these three analytes. Accurate predictions of test solutions, in the range of 12–410 μM for ascorbic acid, 17–530 μM for 4-aminophenol and 10–420 μM for paracetamol, have been achieved with RMSEs lower than 0.10 μM.     

Carbon Paste Electrodes Modified with Graphene Oxides – Comparative Electrochemical Studies of Thioguanine

The voltammetric study of thioguanine (TG) was comparatively investigated on bare, graphene oxide and reduced graphene oxide modified carbon paste electrodes using cyclic (CV) and square wave stripping (SWSV) voltammetric techniques. Depending on the working electrode and pH of supporting electrolyte, characteristic electrochemical behaviour of thioguanine was established and the mechanism of TG oxidation was suggested. Based on the obtained results, the new voltammetric method for TG determination in buffer solutions and pharmaceutical formulation was developed. Atomic force microscopy was used to characterize electrodes surfaces.     

Enhancing chemical analysis with signal derivatization using simple available software packages

Derivative techniques for analytical signal processing are useful for solving some noise and signal resolution problems in various fields of study such as titrimetry, spectrophotometry, chromatography and electrochemistry. The broad use of these techniques, however, is often limited by costly inflexible built-in software packages in commercial analytical instruments. We propose here the application of commercial simple software packages such as Microsoft® Excel and Microcal Origin for signal smoothing and fitting, and for obtaining derivative analytical signals in batch and flow-based analyses, including potentiometric titration, spectrophotometry, chromatography, voltammetry and sequential injection analysis (SIA). The worldwide (especially Excel) software packages are easy-to-use for less experienced users and have also capabilities for advanced users, and therefore employing such packages can result in expansion of useful derivative techniques. We demonstrate application of the available package-aided derivative capabilities for enhancing some chemical analyses, including potentiometric acid–base titration, Bradford assay of protein, chromatographic separation of ajmaline and reserpine and anodic stripping voltammetry of copper. The derivative signals from smoothed and fitted curves offer better accuracy and precision, even for non-resolving peaks and tailing peaks. In some cases, the optimization of experimental conditions is not further required, which can lead to fast method development.     

Portable automated separation system for routine purification and/or pre-concentration of radionuclides based on column chromatography

In recent years the purification and/or pre-concentration of radionuclides before the measurement has grown increasing interest in analytical chemistry. In this study, a new compact and portable stand-alone equipment permitting automatisation of various separation tasks is developed. The new system allows performing quick and reliable automated separation of the selected radionuclide. Since there is no need for permanent manual control of the separation procedures (automatic loading of the sample, washing and stripping solution on the column are controlled via a computer program) the system can be operated overnight. The new system posses the possibility of more variable control for the separation process via new developed user-friendly software, is shielded against the chemical vapors and could be universally equipped with any available chromatographic column. For the automated separation of U, Pu and Am isotopes (achieved recoveries were in the range of 65–95 %, depending on the element separated. The data, presented, show that the application of the module should be also straightforward for other elements: simply by changing the chromatographic columns with the resin having high chemical selectivity for the target ion. The developed separation column module, software and hardware can be readily adapted in any laboratory to meet defined analytical requirements.     

Development and application of computerized battery-powered field programmable data acquisition systems

A computer-based, battery powdered, data acquisition system is described, which forms part of a field-based chemical system for use with sensors generating a voltage. The equipment has been developed using complementary metal oxide semiconductor (CMOS) “low power” integrated circuit technology and is based on a multiplexed bus. One 2k-byte erasable programmable read only memory (EPROM) controls the data acquisition process. Another 2k-byte EPROM contains the monitor program, while a 2k-byte random access memory stores the data before and after manipulation. A microprocessor unit provides all the control signals used by the instrument and data are collected on a real-time basis. The electronics are housed in a self-contained box to which the sensors and an independent keyboard can be connected. The instrument can be linked with as many as eight sensors. With the use of battery-operated CMOS technology, the measurement noise level is low and analytical techniques can be used to determine low concentrations of variables in the field. The viability of the instrument has been demonstrated by obtaining extensive data on the measurement of temperature and pH. Field-based potentiometric titrations, ion-selective electrode applications and studies on battery life are also reported.     

Computer system and flow cell for automated potentiometric and constant-current stripping analysis

A flow cell and a personal computer-based system for potentiometric and constant-current stripping analysis are described. The thin-layer cell is designed for teflon-embedded glassy carbon electrodes in a spring-regulated holder, allowing simple instalment and leak-free behaviour. The personal computer is interfaced to hardware components such as potentiostat, amplifier, peristaltic pump, six inlet valves for different solutions, autosampler and strip-chart recorder. User-accessible commands allow electrolysis, stripping current, pump flow rates, valves, stripping transient recording, derivation, filtration and integration to be controlled, and through a number of user-defined programs, to be performed in unattended operation. This is described by an example. Through a software interface to a high-level language (BASIC), results from any number of analytical runs can be further evaluated by standard addition, or from calibration curves, or by statistical methods.     

Voltammetry as a Virtual Potentiometric Sensor in Modeling of a Metal‐Ligand System and Refinement of Stability Constants. Part 1. Polarographic and Glass Electrode Potentiometric Study of a Dynamic Cd‐Glycine System

A mathematical conversion of data coming from nonequilibrium and dynamic voltammetric techniques (a direct current sampled (DC) and differential pulse (DP) polarography) into potentiometric sensor type of data is described and tested on a dynamic metal‐ligand system. A combined experiment involving DCP, DPP and glass electrode potentiometry (GEP) was performed on a single solution sample containing a fixed [L_T] : [M_T] ratio (acid‐base titration). Dedicated potentiometric software ESTA was successfully employed in the refinement operations performed on virtual potentiometric (VP) data obtained from DC and DP polarography. It was possible to refine stability constants either separately, from VP‐DC or VP‐DP, or simultaneously from any combination of VP‐DC, VP‐DP and GEP. The concept of VP‐DC or VP‐DP is reported for the first time and numerous documented and possible advantages are discussed. The proposed procedure can be easily utilized also by nonelectrochemists who are interested in, e.g., the ligand design strategies.     

Square‐Wave Voltammetry of Cathodic Stripping Reactions. Diagnostic Criteria,Redox Kinetic Measurements,and Analytical Applications

A comparative study of different types of cathodic stripping reactions under conditions of square‐wave voltammetry is presented. Cathodic stripping processes involving reactions of second order as well as reactions coupled by adsorption of the reacting ligand are analyzed The inherent parameters, controlling the overall voltammetric behavior of each cathodic stripping electrode reaction are derived. The criteria for qualitative distinguishing of each mechanism are established as well as a methodology for redox kinetic measurements is proposed. The influence of the parameters of the excitation signal on the properties of the voltammetric response is analyzed in order to find optimal conditions for analytical application. The theoretical results are illustrated by the experiments with a series of uracil derivatives.     

Rapid automatic potentiometric method for analytical control in the manufacture of extraction phosphoric acid

A rapid automatic method for determination of free sulphuric acid in the manufacture of extraction phosphoric acid from apatite has been developed. It is based on potentiometric titration combined with the Gran approach for linearization of the titration curve. The analysis is done with an automatic potentiometric titrator controlled by an HP-85 microcomputer. BASIC software activates the system to perform the data acquisition and calculations, and the whole operation takes only 7-8 min.     

An on-line voltammetric analyzer for trace metals in wastewater

Differential-pulse anodic stripping voltammetric and differential pulse polarographic techniques were adapted to an on-line analytical system to measure trace levels of metals in a waste- water stream. Chromium, nickel, zinc, cadmium, lead and copper were determined automatically for several days to characterize a wastewater stream and detection limits were typically near 50 μg l^?1.     

Integrated system for potentiometric stripping determinations

An automatic system for potentiometric stripping was designed and tested for the determination of lead(II) and cadmium(II) in the 10^?3–10_?6 M range. It consists of solid-state integrated circuitry containing a chemically-sensitive field-effect transistor (CHEMFET) and a transistor control switch. Flow of solutions, application of potentials during the electrode preparation, plating and stripping periods and data acquisition are controlled by a cheap microprocessor. It is shown that 200-μl samples in the concentration range mentioned above can be dealt with in less than 2.5 min with relative standard deviations below 10%. The detection limit of the system is at present restricted by the slow sampling rate of the microprocessor used. The upper value of the usable concentration range is limited by the maximum practical concentration of the oxidant.     

毛细管电泳扫描伏安电化学法分离检测肾上腺素、氯丙嗪和异丙嗪

采用自制的高效毛细管电泳扫描伏安电化学检测装置,在磷酸盐缓冲溶液中进行了肾上腺素、异丙嗪和氯丙嗪的分离检测,在优化的条件下获得了较好的检测重现性和低的检出限。结果表明,采用扫描伏安电化学方法不但能够减少电极的污染,而且可以在电泳过程中获得被测物质的伏安特性及检测体系的动态伏安图,更有利于被测物质的识别。     

Determination of cadmium, lead and copper in milk and milk powder by means of flow potentiometric stripping analysis

A flow potentiometric stripping analysis procedure for the determination of cadmium, lead and copper in milk and milk powder samples is described. The instrumental arrangement consists of a glassy-carbon thin-layer cell through which six different solutions may be drawn by means of a peristaltic pump and magnetically operated valves. The glassy-carbon electrode is pre-coated with a film of mercury which can be employed for several analytical runs. The sample, diluted five-fold with Suprapur hydrochloric acid, is electrolysed for 0.5–4 min prior to stripping in Suprapur hydrochloric acid. Pump-rate, electrolysis time and potential, opening and closing of inlet valves and digital evaluation of stripping times are controlled automatically by the computer. The analytical results agree satisfactorily with the certified values for three milk powder reference samples. The detection limit for cadmium, lead and copper in milk samples after 4, 1 and 0.5 min of pre-electrolysis is 0.8, 4 and 8 μg/l., respectively. An analytical procedure for the determination of lead in samples containing high concentrations of tin is described.     

Applications of nanoscale carbon-based materials in heavy metal sensing and detection

This article reviews applications of nanoscale carbon-based materials in heavy metal sensing and detection. These materials, including single-walled carbon nanotubes, multi-walled carbon nanotubes and carbon nanofibers among others, have unique and tunable properties enabling applications in various fields spanning from health, electronics and the environment sector. Specifically, we highlight the unique properties of these materials that enable their applications in the sorption and preconcentration of heavy metals ions prior to detection by spectroscopic, chromatographic and electrochemical techniques. We also discuss their distinct properties that enable them to be used as novel electrode materials in sensing and detection. The fabrication and modification of these electrodes is discussed in detail and their applications in various electrochemical techniques such as voltammetric stripping analysis, potentiometric stripping analysis, field effect transistor-based devices and electrical impedance are critically reviewed. Perspectives and futures trends in the use of these materials in heavy metal sensing and detection will also be highlighted.     

Development of a microprocessor-based electrochemical instrument interfaced to a microcomputer system for differential-pulse stripping voltammetry in different time domains

An inexpensive, compact microprocessor-based instrument for polarographic and voltammetric analysis has been developed for use in chemically hazardous laboratories, radiation laboratories or clean laboratories. This low-cost unit controls the experiment, collects the data and can be regarded as expendable. The microprocessor-based instrumentation is interface to a microcomputer system, which is external to the laboratory and has all the required peripherals associated with larger laboratory computers. In this institution, four laboratories having the inexpensive microprocessor systems are linked to the larger microcomputer which is housed in an air-conditioned room better suited for computers. A new approach to data collection and evaluation using different time domains in differential-pulse stripping voltammetry is presented as an example of the use of such instrumentation.