Electrochemical cell, voltage concentration dependence

Electrochemical cells are made of two conducting electrodes, called the anode and the cathode. The oxidation reaction takes place at the anode, where electrons are released to flow through a wire to the cathode. At the cathode, reduction takes place. For the oxidation and reduction reactions to occur, the electrodes must be in a conducting solution called an electrolyte. The electrochemical cell voltage depends on the types of materials, usually conducting metals, used as electrodes, and the concentration of the electrolyte solution. (See Figure 6.5.)... 

Electrochemical cells may consist of two electrodes of the same type, but with different concentrations of the electroactive species in the electrolyte. Such cells are known as concentration cells. For example, two platinum electrodes operate in two H+/H2 solutions of different activity, separated by a membrane. The equilibrium cell voltage is defined by Equation (21a). As the standard potential is the same for both electrode reactions, the measurable cell voltage will depend only on the activity ratios, Equation (21b). If in this system both electrolytes were in equilibrium with the same EE pressure, the measured E would respond linearly to the pH difference between the two electrolytes, Equation (21c) (i.e. a pH electrode). 

The position of equilibrium of a reaction maybe affected by changes in the concentration of reagents, temperature and pressure of gases. The voltage of an electrochemical cell will also depend on these factors, so we should use standard conditions when comparing electrode potentials. These are ... 

Each electrochemical couple exhibits a characteristic electrochemical potential and a characteristic Acell voltage C, defined above, depends on the couples combined in a cell and on their concentrations. In order to quantify the properties of electrochemical couples reference electrodes are used. The reference electrode which is primarily used is the standard hydrogen electrode (SHE), or normal hydrogen electrode (NHE). In this case it is an inert Pt electrode around which hydrogen is flushed (see Fig. 3.4). The reaction involved is given by... 

An understanding of the operation of the SECM and an appreciation of the quantitative aspects of measurements with this instrument depends upon an understanding of electrochemistry at small electrodes. The behavior of ultramicroelectrodes in bulk solution (far from a substrate) has been the subject of a number of reviews (17-21). A simplified experimental setup for an electrochemical experiment is shown in Figure 1. The solution contains a species, O, at a concentration, c, and usually contains supporting electrolyte to decrease the solution resistance and insure that transport of O to the electrode occurs predominantly by diffusion. The electrochemical cell also contains an auxiliary electrode that completes the circuit via the power supply. As the power supply voltage is increased, a reduction reaction, O + ne — R, occurs at the tip, resulting in a current flow. An oxidation reaction will occur at the auxiliary electrode, but this reaction is usually not of interest in SECM, since this electrode is placed sufficiently far from the UME... 

Nernst equation An equation stating that the voltage of an electrochemical cell under any conditions depends on the standard cell voltage and the concentrations of the cell components ... 

All electrochemical methods are based on the interaction of electrical energy and matter. The measurements are done in an electrochemical cell where the sample and at least two electrodes are placed. The electrochemical cell possesses a large variety of concentration-dependent physical characteristics that may be exploited for chemical analysis. The methods are mainly used in analysis of aqueous samples but are also applicable to nonaqueous solutions and gases. In most of the methods one concentration-dependent electrical parameter, like voltage, current, resistance, or charge, is measured while the others are kept constant or manipulated to receive the desired response that correlates to the sample composition. 

The majority of solid electrolyte sensors are based on proton conductors (Miura et al. 1989, Alberti and Casciola 2(X)1). Metal oxides that can potentially meet the requirements for application in solid electrolyte sensors are listed in Table 2.7. These proton condnctors typically do not have high porosity but rather can reach 96-99% of the theoretical density (Jacobs et al. 1993). Similar to oxygen sensors, solid-state electrochemical cells for hydrogen sensing are typically constructed by combining a membrane of solid electrolyte (proton conductor) with a pair of electrodes (electronic conductors) Most of the sensors that use solid electrolytes are operated potentiometrically. The voltage produced is from the concentration dependence of the chenucal potential, which at eqnihbrium is represented by the Nemst equation (Eq. 2.3). 

Surely, the difference in the two calculated E values is not a large difference in voltages. But it is an easily measurable one, and for precise measurements the difference can have a big impact on the predicted properties of the ionic solution. For example, it is necessary to consider activity factors when using pH and other ion-selective electrodes, because the exact voltage of the electrochemical cell that is made in the course of the measurement is dependent on the activity of the ions involved, not their concentration. Activity, like fugacity, is a more realistic measure of how real chemical species behave. For precise calculations, activity must be used for ionic solutions, not concentration. 

As noted above, voltage is developed between two electrodes in an electrochemical cell. The voltage depends upon the kinds and concentrations of dissolved chemicals in the solutions contacted by the electrodes. In some cases this voltage can be used to measure concentrations of some substances in solution. This gives rise to the branch of analytical chemistry known as potentiometry. Potentiometry uses ion-selective electrodes or measuring electrodes whose potentials relative to a reference electrode vary with the concentrations of particular ions in solution. The reference electrode that serves as the ultimate standard for potentiometry is the standard hydrogen electrode shown in Figure 8.13. In practice, other electrodes, such as the silver/silver chloride or calomel (mercury metal in contact with are... 

For the measurement of gas components like hydrocarbons (HC) or nitric oxides (NOx) in non-equilibrated gas phases kinetically determined sensors are used (Fig. 19.2 middle).Depending on the electrode material, the gas components do not equilibrate on the measuring electrode at temperatures <700 °C. Thus gas components which are not thermodynamically stable are electrochemically active. In an HC- and 02-containing gas, for example, at least two electrode reactions can take place the electrochemical reduction of oxygen and the electrochemical oxidation of hydrocarbons. The measured open-circuit voltage does not obey the Nemst equation. Therefore such electrode behaviour is often referred to non-Nernstian electrodes (or mixed potential sensors). The cell voltage depends logarithmically on the concentrations of the hydrocarbons ... 

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