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Analytical chemistry studies and uses instruments and methods to separate, identify, and quantify matter. In practice, separation, identification or quantification may constitute the entire analysis or be combined with another method. Separation isolates analytes. Qualitative analysis identifies analytes, while quantitative analysis determines the numerical amount or concentration.
Analytical technique is a method used to determine a chemical or physical property of a chemical substance, chemical element, or mixture. There is a wide variety of techniques used for analysis, from simple weighing to advanced techniques using highly specialized instrumentation.
Cyclic voltammetry (CV) is a type of potentiodynamic electrochemical measurement. In a cyclic voltammetry experiment, the working electrode potential is ramped linearly versus time. Unlike in linear sweep voltammetry, after the set potential is reached in a CV experiment, the working electrode's potential is ramped in the opposite direction to return to the initial potential. These cycles of ramps in potential may be repeated as many times as needed. The current at the working electrode is plotted versus the applied voltage to give the cyclic voltammogram trace. Cyclic voltammetry is generally used to study the electrochemical properties of an analyte in solution or of a molecule that is adsorbed onto the electrode.
A potentiostat is the electronic hardware required to control a three electrode cell and run most electroanalytical experiments. A Bipotentiostat and polypotentiostat are potentiostats capable of controlling two working electrodes and more than two working electrodes, respectively.
Voltammetry is a category of electroanalytical methods used in analytical chemistry and various industrial processes. In voltammetry, information about an analyte is obtained by measuring the current as the potential is varied. The analytical data for a voltammetric experiment comes in the form of a voltammogram which plots the current produced by the analyte versus the potential of the working electrode.
Chronoamperometry is an electrochemical technique in which the potential of the working electrode is stepped and the resulting current from faradaic processes occurring at the electrode is monitored as a function of time. The functional relationship between current response and time is measured after applying single or double potential step to the working electrode of the electrochemical system. Limited information about the identity of the electrolyzed species can be obtained from the ratio of the peak oxidation current versus the peak reduction current. However, as with all pulsed techniques, chronoamperometry generates high charging currents, which decay exponentially with time as any RC circuit. The Faradaic current - which is due to electron transfer events and is most often the current component of interest - decays as described in the Cottrell equation. In most electrochemical cells this decay is much slower than the charging decay-cells with no supporting electrolyte are notable exceptions. Most commonly a three electrode system is used. Since the current is integrated over relatively longer time intervals, chronoamperometry gives a better signal to noise ratio in comparison to other amperometric techniques.
Polarography is a type of voltammetry where the working electrode is a dropping mercury electrode (DME) or a static mercury drop electrode (SMDE), which are useful for their wide cathodic ranges and renewable surfaces. It was invented in 1922 by Czech chemist Jaroslav Heyrovský, for which he won the Nobel prize in 1959. The main advantages of mercury as electrode material are as follows: 1) a large voltage window: ca. from +0.2 V to -1.8 V vs reversible hydrogen electrode (RHE). Hg electrode is particularly well-suited for studying electroreduction reactions. 2) very reproducible electrode surface, since mercury is liquid. 3) very easy cleaning of the electrode surface by making a new drop of mercury from a large Hg pool connected by a glass capillary.
In electrochemistry, overpotential is the potential difference (voltage) between a half-reaction's thermodynamically determined reduction potential and the potential at which the redox event is experimentally observed. The term is directly related to a cell's voltage efficiency. In an electrolytic cell the existence of overpotential implies that the cell requires more energy than thermodynamically expected to drive a reaction. In a galvanic cell the existence of overpotential means less energy is recovered than thermodynamics predicts. In each case the extra/missing energy is lost as heat. The quantity of overpotential is specific to each cell design and varies across cells and operational conditions, even for the same reaction. Overpotential is experimentally determined by measuring the potential at which a given current density is achieved.
Potentiometric titration is a technique similar to direct titration of a redox reaction. It is a useful means of characterizing an acid. No indicator is used; instead the potential is measured across the analyte, typically an electrolyte solution. To do this, two electrodes are used, an indicator electrode and a reference electrode. Reference electrodes generally used are hydrogen electrodes, calomel electrodes, and silver chloride electrodes. The indicator electrode forms an electrochemical half cell with the interested ions in the test solution. The reference electrode forms the other half cell.
In electrochemistry, the Cottrell equation describes the change in electric current with respect to time in a controlled potential experiment, such as chronoamperometry. Specifically it describes the current response when the potential is a step function in time. It was derived by Frederick Gardner Cottrell in 1903. For a simple redox event, such as the ferrocene/ferrocenium couple, the current measured depends on the rate at which the analyte diffuses to the electrode. That is, the current is said to be "diffusion controlled." The Cottrell equation describes the case for an electrode that is planar but can also be derived for spherical, cylindrical, and rectangular geometries by using the corresponding Laplace operator and boundary conditions in conjunction with Fick's second law of diffusion.
Squarewave voltammetry (SWV) is a form of linear potential sweep voltammetry that uses a combined square wave and staircase potential applied to a stationary electrode. It has found numerous applications in various fields, including within medicinal and various sensing communities.
The auxiliary electrode, often also called the counter electrode, is an electrode used in a three electrode electrochemical cell for voltammetric analysis or other reactions in which an electric current is expected to flow. The auxiliary electrode is distinct from the reference electrode, which establishes the electrical potential against which other potentials may be measured, and the working electrode, at which the cell reaction takes place.
Hydrodynamic voltammetry is a form of voltammetry in which the analyte solution flows relative to a working electrode. In many voltammetry techniques, the solution is intentionally left still to allow diffusion controlled mass transfer. When a solution is made to flow, through stirring or some other physical mechanism, it is very important to the technique to achieve a very controlled flux or mass transfer in order to obtain predictable results. These methods are types of electrochemical studies which use potentiostats to investigate reaction mechanisms related to redox chemistry among other chemical phenomenon.
Bulk electrolysis is also known as potentiostatic coulometry or controlled potential coulometry. The experiment is a form of coulometry which generally employs a three electrode system controlled by a potentiostat. In the experiment the working electrode is held at a constant potential (volts) and current (amps) is monitored over time (seconds). In a properly run experiment an analyte is quantitatively converted from its original oxidation state to a new oxidation state, either reduced or oxidized. As the substrate is consumed, the current also decreases, approaching zero when the conversion nears completion.
Instrumental analysis is a field of analytical chemistry that investigates analytes using scientific instruments.
Amperometry in chemistry is detection of ions in a solution based on electric current or changes in electric current.
A liquid metal electrode is an electrode that uses a liquid metal, such as mercury, Galinstan, and NaK. They can be used in electrocapillarity, voltammetry, and impedance measurements.
In electrochemistry, protein film voltammetry is a technique for examining the behavior of proteins immobilized on an electrode. The technique is applicable to proteins and enzymes that engage in electron transfer reactions and it is part of the methods available to study enzyme kinetics.
Electrochemical stripping analysis is a set of analytical chemistry methods based on voltammetry or potentiometry that are used for quantitative determination of ions in solution. Stripping voltammetry have been employed for analysis of organic molecules as well as metal ions. Carbon paste, glassy carbon paste, and glassy carbon electrodes when modified are termed as chemically modified electrodes and have been employed for the analysis of organic and inorganic compounds.
Single-Entity Electrochemistry (SEE) refers to the electroanalysis of an individual unit of interest. A unique feature of SEE is that it unifies multiple different branches of electrochemistry. Single-Entity Electrochemistry pushes the bounds of the field as it can measure entities on a scale of 100 microns to angstroms. Single-Entity Electrochemistry is important because it gives the ability to view how a single molecule, or cell, or "thing" affects the bulk response, and thus the chemistry that might have gone unknown otherwise. The ability to monitor the movement of one electron or ion from one unit to another is valuable, as many vital reactions and mechanisms undergo this process. Electrochemistry is well suited for this measurement due to its incredible sensitivity. Single-Entity Electrochemistry can be used to investigate nanoparticles, wires, vesicles, nanobubbles, nanotubes, cells, and viruses, and other small molecules and ions. Single-entity electrochemistry has been successfully used to determine the size distribution of particles as well as the number of particles present inside a vesicle or other similar structures
References
- ↑ Skoog, Douglas A.; Donald M. West; F. James Holler (1995-08-25). Fundamentals of Analytical Chemistry (7th ed.). Harcourt Brace College Publishers. ISBN 978-0-03-005938-4.
- ↑ Kissinger, Peter; William R. Heineman (1996-01-23). Laboratory Techniques in Electroanalytical Chemistry, Second Edition, Revised and Expanded (2 ed.). CRC. ISBN 978-0-8247-9445-3.
- ↑ Bard, Allen J.; Larry R. Faulkner (2000-12-18). Electrochemical Methods: Fundamentals and Applications (2 ed.). Wiley. ISBN 978-0-471-04372-0.
- ↑ Zoski, Cynthia G. (2007-02-07). Handbook of Electrochemistry. Elsevier Science. ISBN 978-0-444-51958-0.
- ↑ Grundl, Tim (1994-02-01). "A review of the current understanding of redox capacity in natural, disequilibrium systems". Chemosphere. 28 (3): 613–626. Bibcode:1994Chmsp..28..613G. doi:10.1016/0045-6535(94)90303-4.
- ↑ Noyhouzer, T.; Valdinger, I.; Mandler, D. (2013-09-03). "Enhanced Potentiometry by Metallic Nanoparticles". Analytical Chemistry. 85 (17): 8347–8353. doi:10.1021/ac401744w. ISSN 0003-2700. PMID 23947748.
- ↑ H. F. Weber, Wied. Ann., 7, 536, 1879
