Half-reactions electrochemical

Under theoretical cell voltage conditions, for both half-cell reactions (HOR and ORR) there is no net reaction. In other words, both half-electrochemical reactions are in equilibrium, and no net current passes through the external circuit. The cell voltage can be considered the OCV. At 25 °C, if the pressures of both H2 and 02 are 1 atm, the OCV should be 1.23 V. However, in reality the OCV is normally lower and an OCV of 1.23 V is never observed. This is due to the mixed potential at the cathode side, and hydrogen crossover from the anode side to the cathode side [22, 23], At 1.23 V, Pt is not stable so oxidation of Pt occurs ... 

All the reactions listed in Table 4.1 are called half-electrochemical reactions. In reality, if there are no count half-electrochemical reactions to supply electrons, these reactions cannot occur. In an electrochemical cell, there are two half-electrochemical reactions, one is called the anode reaction, and the other is called the cathode reaction. For example, in a H2/O2 fuel cell, there are two half-electrochemical reactions ... 

Note that the two-directional arrows in these reaction expressions indicate that aU these reactions are chemically or electrochemically reversible, although they are not thermodynamically reversible due to their limited reaction rate in both reaction directions. Assuming that these reactions are in equilibrium states, the thermodynamic electrode potentials for the half-electrochemical Reactions (1.1) and (l.II) and the overall Reaction (1. III) can be expressed using the following Nemst equations ... 

In the previous section, we discussed fuel cell thermodynamics. However, in reality, fuel cell operation with an external load is much more practical than in a thermodynamic state. When a H2/air PEM fuel cell outputs power, the half-electrochemical reactions will proceed simultaneously on both the anode and the cathode. The anode electrochemical reaction expressed by Reaction (l.I) will proceed from H2 to protons and electrons, while the oxygen from the air will be reduced at the cathode to water, as expressed by electrochemical Reaction (l.II). For these two reactions, although the hydrogen oxidation reaction (HOR) is much faster than the oxygen reduction reaction (ORR), both have limited reaction rates. Therefore, the kinetics of both the HOR and the ORR must be discussed to achieve a better understanding of the processes occurring in a PEM fuel cell. 

Major components in an electrolyzer are negatively charged cathode electrode, positively charged anode, and electrolyte. The two half electrochemical reactions and the overall reaction are as follows ... 

Redox flow batteries, under development since the early 1970s, are stUl of interest primarily for utility load leveling applications (77). Such a battery is shown schematically in Figure 5. Unlike other batteries, the active materials are not contained within the battery itself but are stored in separate tanks. The reactants each flow into a half-ceU separated one from the other by a selective membrane. An oxidation and reduction electrochemical reaction occurs in each half-ceU to generate current. Examples of this technology include the iron—chromium, Fe—Cr, battery (79) and the vanadium redox cell (80). 

The overall reaction describes what goes on in the entire electrochemical cell. In half of the cell, the right beaker, reaction (7) occurs. In the other half of the cell, the left beaker, reaction (2) occurs. Hence, reactions (7) and (2) are called half-cell reactions or half-reactions. 

Ab initio atomic simulations are computationally demanding present day computers and theoretical methods allow simulations at the quantum mechanical level of hundreds of atoms. Since an electrochemical cell contains an astronomical number of atoms, however, simplifications are essential. It is therefore obvious that it is necessary to study the half-cell reactions one by one. This, in turn, implies that a reference electrode with a known fixed potential is needed. For this purpose, a theoretical counterpart to the standard hydrogen electrode (SHE) has been established [Nprskov et al., 2004]. We will describe this model in some detail below. 

Here, the last term accounts for the excess ions in the interfacial region, which compensate the excess charge on the electrode surface and keep the overall interface electroneutral. What in electrochemical terms is often described as a polarizable active electrode and an unpolarizable reference electrode ensures that any change of the number of ions in the electrochemical half-cell under consideration, caused by an electrochemical reaction, is just compensated by a corresponding counter-reaction at the reference electrode. 

In case (c), a voltage opposite to and higher than the emf of the galvanic cell is imposed as a consequence, the current flow and hence also the electrochemical reactions are reversed, which means that half-reaction 1 becomes an anodic oxidation and half-reaction 2 is a cathodic reduction, so that Zn is deposited instead of Cu. 

The electrochemical cell can again be of the regenerative or electrosynthetic type, as with the photogalvanic cells described above. In the regenerative photovoltaic cell, the electron donor (D) and acceptor (A) (see Fig. 5.62) are two redox forms of one reversible redox couple, e.g. Fe(CN)6-/4 , I2/I , Br2/Br , S2 /S2, etc. the cell reaction is cyclic (AG = 0, cf. Eq. (5.10.24) since =A and D = A ). On the other hand, in the electrosynthetic cell, the half-cell reactions are irreversible and the products (D+ and A ) accumulate in the electrolyte. The most carefully studied reaction of this type is photoelectrolysis of water (D+ = 02 and A = H2)- Other photoelectrosynthetic studies include the preparation of S2O8-, the reduction of C02 to formic acid, N2 to NH3, etc. 

The pe and Eh are equivalent electrochemical descriptions of oxidation state for a system in equilibrium. For an aqueous solution, any half-cell reaction... 

A reaction in an electrochemical cell comprises two half-cell reactions. Even when we want to focus on a single half-cell, we must construct a whole cell and determine its cell emf, which is dehned as (positive electrode) - E(negative electrode) - Only when we know both the emf and the value of one of the two electrode potentials can we calculate the unknown electrode potential. 

Electrode reactions are inner-sphere reactions because they involve adsorption on electrode surfaces. The electrode can act as an electron source (cathode) or an electron sink (anode). A complete electrochemical cell consists of two electrode reactions. Reactants are oxidized at the anode and reduced at the cathode. Each individual reaction is called a half cell reaction. The driving force for electron transfer across an electrochemical cell is the Gibbs free energy difference between the two half cell reactions. The Gibbs free energy difference is defined below in terms of electrode potential,... 

Electrochemical reactions involve redox reactions. Redox is a term that stands for reduction and oxidation. Reduction is the gain of electrons and oxidation is the loss of electrons. For example, if you place a piece of zinc metal in a solution containing the Cu2+ ion. A reddish solid forms on the surface of the zinc metal. That substance is copper metal. At the molecular level, the zinc metal is losing electrons to form the Zn2+ cation and the Cu2+ ion is gaining electrons to form copper metal. These two processes (called half-reactions) are ... 

We will illustrate the above point with the following example. Consider the cell Zn I ZnS04(aq) 11 CuS04(aq) Cu, which is commonly called the Daniell cell. The actual process of cell discharge involves an electrochemical reaction at both electrodes. Since the zinc is the more negative of the two half cells, oxidation would occur on the zinc side of the cell, as follows ... 

Equations 7.2 and 7.3 are examples of electrochemical half-cell reactions. Since free electrons are not found in nature, half-cell reactions always occur in pairs such that the electrons generated by one are consumed by the other. The half-cell reaction that releases electrons is referred to as an oxidation reaction. The half-cell reaction that consumes electrons is referred to as a reduction reaction. For the redox reaction shown in Eq. 7.1, the oxidation and reduction half-cell reactions are given by Eqs. 7.2 and 7.3,... 

When two interval scales are used to measure the amount of change in the same property, the proportionality of differences is preserved from one scale to the other. For example. Table 1.4 shows reduction potentials of three electrochemical half-cell reactions measured in volts with reference to the standard hydrogen electrode (SHE, E°) and in millivolts with reference to the standard silver-silver chloride electrode (Ag/AgCl, ). For the SHE potentials the proportion of differences between the intervals +0.54 to +0.80 and +0.34 to +0.80 is... 

A fuel cell is a device that converts the free energy change of a chemical reaction directly into electrical energy. This conversion occurs by two electrochemical half cell reactions. 

The two half reactions of any redox reaction together make up an electrochemical cell. This cell has a standard potential difference, E , which is the voltage of the reaction at 25 °C when all substances involved are at unit activity. E refers to the potential difference when the substances are not in the standard state. E for a particular reaction can be found by subtracting one half cell reaction from the other and also subtracting the corresponding voltages. For example for reduction of Fe to Fe by H2, E° = 0.77 - 0 = 0.77 V. A further example is the oxidation of Fe " by solid Mn02 in acid solution. The half cell reactions are. 

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