Electroanalytical methods

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Electroanalytical methods are a class of techniques in analytical chemistry which study an analyte by measuring the potential (volts) and/or current (amperes) in an electrochemical cell containing the analyte. [1] [2] [3] [4] These methods can be broken down into several categories depending on which aspects of the cell are controlled and which are measured. The three main categories are potentiometry (the difference in electrode potentials is measured), amperometry (electric current is the analytical signal), coulometry (charge passed during a certain time is recorded).

Contents

Potentiometry

Potentiometry passively measures the potential of a solution between two electrodes, affecting the solution very little in the process. One electrode is called the reference electrode and has a constant potential, while the other one is an indicator electrode whose potential changes with the sample's composition. Therefore, the difference in potential between the two electrodes gives an assessment of the sample's composition. In fact, since the potentiometric measurement is a non-destructive measurement, assuming that the electrode is in equilibrium with the solution, we are measuring the solution's potential. Potentiometry usually uses indicator electrodes made selectively sensitive to the ion of interest, such as fluoride in fluoride selective electrodes, so that the potential solely depends on the activity of this ion of interest. The time that takes the electrode to establish equilibrium with the solution will affect the sensitivity or accuracy of the measurement. In aquatic environments, platinum is often used due to its high electron transfer kinetics, [5] although an electrode made from several metals can be used in order to enhance the electron transfer kinetics. [6] The most common potentiometric electrode is by far the glass-membrane electrode used in a pH meter.

A variant of potentiometry is chronopotentiometry which consists in using a constant current and measurement of potential as a function of time. It has been initiated by Weber. [7]

Amperometry

Amperometry indicates the whole of electrochemical techniques in which a current is measured as a function of an independent variable that is, typically, time (in a chronoamperometry) or electrode potential (in a voltammetry). Chronoamperometry is the technique in which the current is measured, at a fixed potential, at different times since the start of polarisation. Chronoamperometry is typically carried out in unstirred solution and at the fixed electrode, i.e., under experimental conditions avoiding convection as the mass transfer to the electrode. On the other hand, voltammetry is a subclass of amperometry, in which the current is measured by varying the potential applied to the electrode. According to the waveform that describes the way how the potential is varied as a function of time, the different voltammetric techniques are defined.

Chronoamperometry

In a chronoamperometry, a sudden step in potential is applied at the working electrode and the current is measured as a function of time. [8] Since this is not an exhaustive method, microelectrodes are used and the amount of time used to perform the experiments is usually very short, typically 20 ms to 1 s, as to not consume the analyte.

Voltammetry

A voltammetry consists in applying a constant and/or varying potential at an electrode's surface and measuring the resulting current with a three-electrode system. This method can reveal the reduction potential of an analyte and its electrochemical reactivity. This method, in practical terms, is non-destructive since only a very small amount of the analyte is consumed at the two-dimensional surface of the working and auxiliary electrodes. In practice, the analyte solution is usually disposed of since it is difficult to separate the analyte from the bulk electrolyte, and the experiment requires a small amount of analyte. A normal experiment may involve 1–10 mL solution with an analyte concentration between 1 and 10 mmol/L. More advanced voltammetric techniques can work with microliter volumes and down to nanomolar concentrations. Chemically modified electrodes are employed for the analysis of organic and inorganic samples.

Polarography

Polarography is a subclass of voltammetry that uses a dropping mercury electrode as the working electrode.

Coulometry

Coulometry uses applied current or potential to convert an analyte from one oxidation state to another completely. In these experiments, the total current passed is measured directly or indirectly to determine the number of electrons passed. Knowing the number of electrons passed can indicate the concentration of the analyte or when the concentration is known, the number of electrons transferred in the redox reaction. Typical forms of coulometry include bulk electrolysis, also known as Potentiostatic coulometry or controlled potential coulometry, as well as a variety of coulometric titrations.

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<span class="mw-page-title-main">Analytical chemistry</span> Study of the separation, identification, and quantification of matter

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.

<span class="mw-page-title-main">Cyclic voltammetry</span> Method of analyzing electrochemical reactions

In electrochemistry, cyclic voltammetry (CV) is a type of potentiodynamic 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.

Differential pulse voltammetry (DPV) is a voltammetry method used to make electrochemical measurements and a derivative of linear sweep voltammetry or staircase voltammetry, with a series of regular voltage pulses superimposed on the potential linear sweep or stairsteps. The current is measured immediately before each potential change, and the current difference is plotted as a function of potential. By sampling the current just before the potential is changed, the effect of the charging current can be decreased.

<span class="mw-page-title-main">Reference electrode</span> Electrode with a stable and accurate electrode potential

A reference electrode is an electrode that has a stable and well-known electrode potential. The overall chemical reaction taking place in a cell is made up of two independent half-reactions, which describe chemical changes at the two electrodes. To focus on the reaction at the working electrode, the reference electrode is standardized with constant concentrations of each participant of the redox reaction.

<span class="mw-page-title-main">Potentiostat</span> Electronic system controlling a three electrode cell

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.

<span class="mw-page-title-main">Voltammetry</span> Method of analyzing electrochemical reactions

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.

<span class="mw-page-title-main">Chronoamperometry</span> Analytical method in electrochemistry

In electrochemistry, chronoamperometry is an analytical technique in which the electric 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.

<span class="mw-page-title-main">Polarography</span> Method of chemical analysis

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 Czechoslovak 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.

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.

In electrochemistry, 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.

In analytical chemistry, 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.

<span class="mw-page-title-main">Instrumental chemistry</span> Study of analytes using scientific instruments

Instrumental analysis is a field of analytical chemistry that investigates analytes using scientific instruments.

Amperometry in chemistry is the 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.

<span class="mw-page-title-main">Fast-scan cyclic voltammetry</span> Method of chemical analysis

Fast-scan cyclic voltammetry (FSCV) is cyclic voltammetry with a very high scan rate (up to 1×106 V·s−1). Application of high scan rate allows rapid acquisition of a voltammogram within several milliseconds and ensures high temporal resolution of this electroanalytical technique. An acquisition rate of 10 Hz is routinely employed.

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.

<span class="mw-page-title-main">Electrochemical stripping analysis</span> Method of chemical analysis

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.

References

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Bibliography