Potentiometry with current flow

These methods are divided into potentiometry with zero current (classical potentiometry) and potentiometry with current flow. 

With no current through the electrolytic cell, it does not matter whether the electrodes are large or small the equilibrium potentials are the same. But with current flow, the current density and therefore the voltage drop and the polarization, will he much higher at the small electrode. An increased potential drop will occur in the constrictional current path near the small electrode, and in general the properties of the small electrode will dominate the results. The small electrode will be the electrode studied, often called the working electrode. It is a monopolar system, meaning that the effect is determined hy one electrode. The other electrode becomes the indifferent or neutral electrode. Note that this division is not true in potentiometry, electrode area is unimportant under no-current conditions. 

Potentiometry is a method of obtaining chemical information by measuring the potential of an indicator electrode under zero current flow. It is based on the Nernst equation, which expresses the electrode potential as a function of the activity (or activities) of the chemical species in solution. The information obtained varies with indicator electrode, from the activity (concentration) of a chemical species to the redox potential in the solution. The potential of the indicator electrode is measured against a reference electrode using a high inptit-impedance mV/pH me-... 

Although electrochemistry has the stigma of being difficult to use, and therefore is often overlooked as an analysis option, potentiometric measurements are probably the most common technique encountered. Many analytical chemists make potentiometric measurements daily, whenever they use a pH meter. Potentiometry is based on the measurement of the potential between two electrodes immersed in a test solution. As the electrical potential of the cell is measured with no current flow between the electrodes, potentiometry is an equilibrium technique. The first electrode, the indicator electrode, is chosen to respond to the activity of a specific species in the test solution. The second electrode is a reference of known and fixed potential. The design of the indicator electrode is fundamental to potentiometric measurements, and should interact selectively with the analyte of interest so that other sample constituents do not interfere with the measurement. Many different strategies have been developed to make indicator electrodes that respond selectively to a number of species including organic ions. 

Electrochemical methods are increasingly popular in the clinical laboratory, for measurement not only of electrolytes, blood gases, and pH but also of simple compounds such as glucose. Potentiometry is a method in which a voltage is developed across electrochemical cells as shown in Figure 27.3. This voltage is measured with little or no current flow. 

Potentiometry Measurement of the potential produced by electrochemical cells under equilibrium conditions with no current flow. 

With an external DC power supply connected to the electrolytic cell, the applied voltage that gives no DC current flow in the external circuit corresponds to the equilibrium potential of the half-cell (or actually the cell). It is the same voltage as read by a voltmeter with very high input resistance and virtually no current flow (pH meter). In electrochemistry, potentiometry is to measure the potential of an electrode at zero current flow, which is when the cell is not externally polarized. To understand the equilibrium potential with zero external current, we must introduce the concept of electrode reaction... 

In parallel with these current flow-based measurements (equilibrium) potentiometry held an important position/" particularly after introduction of all the various types of ion-sensitive membranes whereas conductometry, oscillometry, and dielectrometry were an occasional choice and nearly the same can be said about some other measurements (e.g. biamperometry and bipotentiometry, chronoamperometry and chronopotentiometry ). In the last half century, other techniques were proposed, such as sonovoltammetry, electro... 

Indeed, while potentiometry refers to a static system, in which no reaction takes place, the current flow in controlled potential techniques is the cause of occurrence of a redox reactiOTi the electrode potential is imposed by an external source and eventually changes with time. Considering what happens at WE, reversibility... 

Whereas potentiometry uses an experimental approach with a minimum current flow, the voltametric setup involves a galvanostat and measures potential differences with a predefined constant current. In this case electrochemical processes at the electrode surface provide the generation of electric charge thus the working electrodes are basically the same as the ones for voltammetric and amperometric measurements (see below). Depletion of an electroactive species causes the galvanostat to increase the potential to keep up a constant current flow. 

In electrochemical detection, the potential of a working electrode can be measured versus a reference electrode, usually while no net current is flowing between the electrodes. This type of detection is referred to as potentiometry. Alternatively, a potential is applied to the working electrode with respect to the reference electrode while the generated oxidation or reduction current is measured. This technique is referred to as amperometry. When applying a negative po-... 

For decades the electrochemical techniques, i.e., potential, current, or charge step methods such as chronoamperometry, -r chronocoulometry, chrono-potentiometry, coulostatic techniques were considered as fast techniques, and only with other pulse techniques such as temperature jump (T-jump) introduced by Eigen [i] or flash-photolysis method invented by Norrish and Porter [ii], much shorter time ranges became accessible. (For these achievements Eigen, Norrish, and Porter shared the 1964 Nobel Prize.) The advanced versions of flash-photolysis allow to study fast homogeneous reactions, even in the picosecond and femtosecond ranges [hi] (Zewail, A.H., Nobel Prize in Chemistry, 1999). Several other techniques have been elaborated for the study of rapid reactions, e.g., flow techniques (stopped-flow method), ultrasorhc methods, pressure jump, pH-jump, NMR methods. 

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